A 32 bit architecture does not necessarily use 32 bit long instructions. The 32 bit only tells you, that memory addresses are 32 bit long so 232 addresses are possible (232 Byte = 4GiB) and registers can store equally many bits.
Instructions can have variable length depending on your architecture.
For example if you have an x86 architecture (16, 32 or 64 bit), instructions have a variable length. The maximum length is theoretically unlimited. In the real world, instructions on x86 machines are limited to 15 bytes. (See this answer)
If the 15 byte limit applies, the minimum number of instructions, which can be stored in a 256 Byte memory unit is ⌊256/15⌋=17 instructions.
The shortest possible instructions on an x86 machine are just 1 Byte long, so 256 instructions would fit. (x86 Wikipedia article)
If you are using a RISC architecture (reduced instruction set), often instructions do have a fixed length. For example, the ARM architecture initially used only 32 bit instructions, so 256/4=64 instructions would fit into your memory unit. Current versions of ARM (32 bit or 64 bit) have 32 and 16 bit long instructions to increase code density, so up to 128 instructions could theoretically fit in your memory unit. (ARM Wikipedia article)