Fluttershy tries "The Stare" on an uncooperative Discord in chapter 3. He smugly shrugs it off, seeming unaffected. Then, as soon as she leaves the room...
Discord made sure that the pegaus was out of sight and earshot, then promptly let his ears fall back and his eyes to go wide. He grimaced, rubbing his chilled shoulders with crossed arms, the stare still fresh in his mind and probably would be for ages. "Guh."
Especially funny when you consider his Canon!reaction in "Keep Calm and Flutter On".
The scene in which Rarity discovers that Fluttershy has made her "ponysit" Discord counts. Especially Discord's greeting to Rarity.
Discord: Why hellooo, Rarity! Seen your old flame Tom lately? If not I found a pebble the other day that you'd die for! He's a little small, but does size matter to you?"
As of Chapter 16, Discord now has a pet chicken. He names it Barbara. Of course, Discord being Discord he he gives the chicken the ability to moo instead of cluck. He than proceeds to sing duets with it.
Funny because of Mood Whiplash: In the previous chapter, Discord has just saved Luna from a collapsing cave, and "Barbara" just waltzed into the cave while the two were trapped.
Also worth mentioning is the method that Discord uses to save Luna in the cave when she's trapped underneath a giant boulder, he turns the boulder into jello.
In Chater 6 of the sequel Distorted Worlds, while Discord was talking to and being like a five-year-old to his father, who is really a siren about to feed off of him, it inwardly groaned and vowed to stick to easier victims, like pigeons.