What do you call words that look like they should rhyme, but don't? An eye rhyme. "The tough coughs as he ploughs the dough," as Dr. Seuss said. And this puzzle is replete with examples, from the title, to the theme answers' clues, to the theme answers themselves. I love the execution here. That's 19 total eye rhymes used, but better, 9 of them are used to clue another 9, and that's quite clever.
Unfortunately, while the clues are fun in their couplet form, the actual answers fall kind of flat in my opinion. The only one that made me chuckle at all (and it was a fairly weak sort of chuckle) was BASELINEVASELINE. That's an amusing image. Otherwise they were fairly mundane.
But that's okay. I enjoyed the process of coming across each new one. Once I'd figured out the pattern, it made filling in the puzzle much easier: with a few crosses, I had more than half the theme answer filled because of the eye rhyme.
Given the density of theme material, there is a ton of interesting long fill. 16D: One working on the board? (PROSURFER) is cute. I also liked ACTUALSIZE. 40D: [!!!] (IMSHOCKED) is nicely done.
I was mildly confused by the cross reference between GUACAMOLE and TACOS, reading the clue for the latter as being what you'd serve to go with the "Party bowlful" of 76D, instead of just stuff that is often served with the dip. I was all ready to get up in arms about it, but talked myself off of the ledge. Whew!
I love the symmetric pairing of 45A: Cry to a cop (ARRESTHIM) and 88A: "Just be cool" (ACTCASUAL). Seems like the setup for a movie scene.
78D: "://" preceder (HTTP). I really really wanted this to be an emoticon. I had to get several crosses to convince me otherwise.
1A: Like the 30 Rock building (DECO) - C-. It's Art Deco.
Fave: SCHNOZ (90A: Hooter or honker). Great answer, great clue.
Least fave: MOOC (Acronym for a class taught over the internet). Stands for "massively open online course".