A friend of mine downloaded some malware from Facebook, and I'm curious to see what it does without infecting myself. I know that you can't really decompile an .exe, but can I at least view it in Assembly or attach a debugger?
Edit to say it is not a .NET executable, no CLI header.
With a debugger you can step through the program assembly interactively.
With a disassembler, you can view the program assembly in more detail.
With a decompiler, you can turn a program back into partial source code, assuming you know what it was written in (which you can find out with free tools such as PEiD - if the program is packed, you'll have to unpack it first OR Detect-it-Easy if you can't find PEiD anywhere. DIE has a strong developer community on github currently).
Some related tools that might come handy in whatever it is you're doing are resource editors such as ResourceHacker (free) and a good hex editor such as Hex Workshop (commercial).
Additionally, if you are doing malware analysis (or use SICE), I wholeheartedly suggest running everything inside a virtual machine, namely VMware Workstation. In the case of SICE, it will protect your actual system from BSODs, and in the case of malware, it will protect your actual system from the target program. You can read about malware analysis with VMware here.
Personally, I roll with Olly, WinDbg & W32Dasm, and some smaller utility tools.
Also, remember that disassembling or even debugging other people's software is usually against the EULA in the very least :)