ARM is similar, ARM processors define a word as 32-bits, even on 64-bit ARM processors, but they are also byte addressable.
As best as I can tell, it seems like a word is whatever the size of the arithmetic or general purpose register is at the time that the processor was introduced, and even if later a new processor is introduced with larger registers, for backwards compatibility the size of a word remains the same.
Lots of CISC architectures allow memory accesses in various units even if they call general-purpose-register-sized quantities "word".
Iirc the C standard specifies that all memory can be accessed via char*.
Some hardware may raise an exception if you attempt to retrieve a value at an address that is not a (greater than 1) multiple of a byte, but that has no bearing on the definition of a byte.