It seems there are a bunch of humanoid males, it's just that they don't get much screen time. I wonder if there's any in-story reason for all of Reimu's adversaries being female though.
I remember reading someplace that it's because females are in touch with the anima, i.e. spirits and magic and h4x and etc. That's why they can {read minds, manipulate fate, shoot giant magic lasers}, and that's what makes them remotely interesting or powerful enough to be in million-bullet wars.
Considering this sort of thing has always been a part of animistic religions, this actually makes sense by ZUN standards.
I'm surprised this question didn't come up: How did Byakuren get spell cards? Mary Sue Reimu (maRei Mu) canonically created the system long after Byakuren was stuffed into Hokkai, so...