This episode is when they first meet. In Blame It on the Alcohol, Santana and Blaine go to Rachel's party with the rest of the New Directions. While Blaine is singing Don't You Want Me with Rachel, Santana sings along to the words, "I want you, I do," possibly with the intention of it being directed back towards him, though it could have been directed to Rachel.
The Santana-Blaine relationship changes from just acquaintance to a friendship. When Dave starts making negative gay comments towards Blaine and Kurt in the hallway, Santana shows up and threatens Karofsky with physical violence: "I have razor blades hidden in my hair." Intimidated and bewildered, Karofsky leaves. Blaine then says to Santana, with a slight smile "We could've handled that," she replies with a smile and says "It was more fun doing it together." Santana receives a tweet on her phone and leaves Blaine looking on, amused.
Kurt, Blaine, Santana, Mercdes, and Tina are seen discussing Nationals at the Lima Bean. Where Santana, wanders off in her thoughts of becoming Prom Queen, and while leaving she mistakenly says "I've got to gay" soon correcting herself with "I've got to go." She walks off, and Blaine is seen grinning at what she said.
While Blaine is singing It's Not Unusual in the McKinley courtyard, Santana turns around from her table, smiles and makes a hand gesture towards the Cheerios to start dancing with Blaine. She soon gets up with the rest of the Cheerios and starts dancing with Blaine. They both smile at each other, but Santana's smile seems more devious than Blaine's. Without Blaine's knowledge, Santana has the Cheerios pour lighter fluid on the piano causing it to go up in flames when Quinn flicks a lit cigarette onto it, leaving Blaine confused and shocked. Later in the choir room she corrects Finn on who started the fire when he attacked Blaine for it.
During Blaine's performance of Last Friday Night, Santana gives Blaine dirty and weird looks throughout the performance, she also refuses to participate in it, even though everyone else seems to be dancing and having fun. After, Santana is mad because she claims New Directions is going to become the "Rachel and Blaine show" now that Mercedes is gone. Santana is also the only member of the New Directions who does not participate in the musical number.
Blaine and Kurt try and console Santana about her recent outing. She makes a comment to Blaine about his sense of fashion, telling him to lay off the bow ties, she then tells them that she will add Perfect to the list of crap she has been through in her life.
Santana and Blaine are seen discussing Michael Jackson at the Lima Bean, and later seen together in a parking garage during Bad. Santana also appears to be upset about Blaine's eye surgery and goes to Dalton Academy because she wants to find out what Sebastian put in the slushie. After a duel between them singing Smooth Criminal he admits that he put rock salt in it.
During a scene at The Lima Bean, Blaine asks Brittany how Santana is.
Blaine mentions Santana during a conversation with Brittany while they are talking about their respective lovers (Santana and Kurt).
To get Sam out of his funk, Blaine organizes a video full of support from individuals that Sam had somehow impacted and changed their lives significantly. Since Santana appeared in the video, it is implied that Blaine personally reached out to her for help.
Blaine is seen enjoying Santana's Nutbush City Limits performance.
Sang Together (In a Group Number)
|Do They Know It's Christmas?||Extraordinary Merry Christmas||Finn, Rachel, Mercedes, Artie, Brittany, Puck, Tina and Kurt|
|Bad||Michael||Artie and Sebastian|
|Fly/I Believe I Can Fly||On My Way||Rachel, Finn, Mercedes and Artie|
|Paradise by the Dashboard Light||Nationals||Rachel, Finn, Mercedes, Puck, Brittany, Mike and Kurt|
|The Scientist||The Break-Up||Rachel, Finn, Brittany, Kurt, Will and Emma|
|You're The One That I Want||Glease||Rachel, Finn, Brittany, Kurt, Marley and Ryder|
|We've Got Tonite||I Do||Finn, Rachel, Quinn, Kurt, Artie, Marley, Jake and Betty|
|Mamma Mia||Guilty Pleasures||Rachel, Kurt, Kitty, Marley, Sam and Unique|
- It's Not Unusual by Tom Jones. (The Purple Piano Project)
- Last Friday Night by Katy Perry (Pot O' Gold)
- Perfect by P!nk. (I Kissed a Girl)
- They both are able to rap, as shown in Fly/I Believe I Can Fly. (On My Way)
- They were both slushied by Sebastian in the same episode. (Michael)
- Their respective partners have kissed each other. (Brittany and Kurt)
- They are both gay.
- Karofsky has made negative comments towards both of them in the past.
- During the two different senior class president elections, they both have something to do with Brittany. (Blaine runs against Brittany in Makeover, and Santana campaigns with Brittany in I Am Unicorn)
- They were both on the Cheerios
- They have both been captains of the Cheerios.
- They have both liked Sam in the past.