Sooooooo, I've figured out what characters the first 75 chapters of MLB are going to be about. They are as followed:

1 Rainbow Dash
2 Nysa
3 Twilight Sparkle
4 Rarity
5 Fluttershy
6 Pinkie Pie
7 Applejack (This will be Applebloom and Big Mac's backstory as well. Sorry to anyone hoping for these characters getting their own)
8 Luna
9 Discord
10 Cadence
11 Celestia
12 Derpy
13 Lyra
14 Vinyl Scratch (DJ-Pon3)
15 Dr. Whooves
16 Octavia
17 Bon Bon
18 Sombra
19 Crisalyss

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