It depends on the betta. Some live quite happily with other fish, as Resa's Rafe. Others are so aggressive they even attack snails. And because yours has been in the tank on his own, he may object to 'invaders' in his territory. It is safer to add the betta last so he sees the other fish as part of the scenery rather than invaders.
The types of fish that
usually do OK with bettas are:
bottom dwellers
fish with short fins and tails
fish in monochrome or subdued colours
fish that do not ever nip fins. Those that sometimes do can't help themselves when the see a betta's fins.
fish that are big enough not be regarded as a snack
Cories tick all those boxes
With your 64 litre, you would need to look at dwarf cories - pygmy, salt & pepper (habrosus, not peppered cories) and hastatus, or possibly the slightly bigger pandas.
Harlequin rasboras, or one of their smaller look-alikes. Those are Trigonostigma hengeli (copper rasbora, and a few other common names) and T. espei (lambchop rasbora, slender rasbora). These fall into the non-nippy and subdued colour categories.
Endlers, male and female. Although they are brightly coloured, male endlers have short fins and tails and can swim faster than a betta. And any nippiness of the endlers is kept exclusively among themselves. Mine don't notice the other fish in the tank! And the betta would keep any population explosion under control.
But to be honest, if it was me, I'd put the betta in the 25 litre then you woudn't be restricted in the 64 litre. My bettas have always been in 25-ish litre tanks with just a small nerite snail for company (bee nerites, horned nerites). I did have one in a 50 litre tank with pygmy cories and female endlers until he developed a growth that I was worried might be infectious, so I moved him out. He was fine with those fish.