`.format` lets you dereference arbitrary attributes and indices (I don't think it lets you call methods though), meaning you can run code and exfiltrate data through translated strings if they're not extremely carefully reviewed, which they often are not.
% only lets you format the values you're given.
> and isn't something like Django's _(str) better anyway
They're orthogonal. You apply string formatting after you get the translated pattern string from gettext. In fact, Django's own documentation demonstrates this:
def my_view(request, m, d):
output = _('Today is %(month)s %(day)s.') % {'month': m, 'day': d}
return HttpResponse(output)