for an unmanaged dll you need to first check if it is a 16bit dll (hopefully not)
Then check the IMAGE_FILE_HEADER.Machine field.
Someone else took the time to work this out already so I will just repeat here
To distinguish between 32bit and 64 bit PE file, you should check
IMAGE_FILE_HEADER.Machine field. Based on the Microsoft PE and COFF
Specification below, I have listed out
all the possible values for this field:
http://download.microsoft.com/download/9/c/5/9c5b2167-8017-4bae-9fde-d599bac8184a/pecoff_v8.doc
IMAGE_FILE_MACHINE_UNKNOWN 0x0 The contents of this field are assumed to be applicable to any machine type
IMAGE_FILE_MACHINE_AM33 0x1d3 Matsushita AM33
IMAGE_FILE_MACHINE_AMD64 0x8664 x64
IMAGE_FILE_MACHINE_ARM 0x1c0 ARM little endian
IMAGE_FILE_MACHINE_EBC 0xebc EFI byte code
IMAGE_FILE_MACHINE_I386 0x14c Intel 386 or later processors and compatible processors
IMAGE_FILE_MACHINE_IA64 0x200 Intel Itanium processor family
IMAGE_FILE_MACHINE_M32R 0x9041 Mitsubishi M32R little endian
IMAGE_FILE_MACHINE_MIPS16 0x266 MIPS16
IMAGE_FILE_MACHINE_MIPSFPU 0x366 MIPS with FPU
IMAGE_FILE_MACHINE_MIPSFPU16 0x466 MIPS16 with FPU
IMAGE_FILE_MACHINE_POWERPC 0x1f0 Power PC little endian
IMAGE_FILE_MACHINE_POWERPCFP 0x1f1 Power PC with floating point support
IMAGE_FILE_MACHINE_R4000 0x166 MIPS little endian
IMAGE_FILE_MACHINE_SH3 0x1a2 Hitachi SH3
IMAGE_FILE_MACHINE_SH3DSP 0x1a3 Hitachi SH3 DSP
IMAGE_FILE_MACHINE_SH4 0x1a6 Hitachi SH4
IMAGE_FILE_MACHINE_SH5 0x1a8 Hitachi SH5
IMAGE_FILE_MACHINE_THUMB 0x1c2 Thumb
IMAGE_FILE_MACHINE_WCEMIPSV2 0x169 MIPS little-endian WCE v2
Yes, you may check
IMAGE_FILE_MACHINE_AMD64|IMAGE_FILE_MACHINE_IA64 for 64bit and IMAGE_FILE_MACHINE_I386 for 32bit.