There is an easy way to do this with CorFlags. Open the Visual Studio Command Prompt and type "corflags [your assembly]". You'll get something like this:
c:\Program Files (x86)\Microsoft Visual Studio 9.0\VC>corflags "C:\Windows\Microsoft.NET\Framework\v2.0.50727\System.Data.dll"
Microsoft (R) .NET Framework CorFlags Conversion Tool. Version 3.5.21022.8 Copyright (c) Microsoft Corporation. All rights reserved.
Version : v2.0.50727 CLR Header: 2.5 PE : PE32 CorFlags : 24 ILONLY : 0 32BIT : 0 Signed : 1
You're looking at PE and 32BIT specifically.
Any CPU:
PE: PE32
32BIT: 0
x86:
PE: PE32
32BIT: 1
x64:
PE: PE32+
32BIT: 0