Yes, the reason is that you need 64 characters if you want each character to encode 6 bits as log2(64) == 6. If you only have 63 characters in your alphabet then one of your 6-bit combinations has no character to represent it.
Base32 can represent 5 bits per character because log2(32) == 5. Anything in between 32 and 64 doesn't buy you anything because there is no integer between 5 and 6.