Check out depends (Dependency Walker). It's great for this.
It not only identifies what the DLL relies upon (ie if you have a problem loading a program and it specifies an invalid DLL or missing reference, this program lets you figure out what you are missing... visual C++, .net, etc).
But it also allows you to view the native assembly Exports. This means you can call the functions of the DLL after loading it using their exported address. Very easy.
The only hard part is knowing a.) What the functions do, and b.) How to use them.
And for that, you are best using a debugger like OllyDbg to load the assembly, and step through a function's execution.
All of the above answers are good as well. I just wanted to tell you about Depends, because it's incredibly useful, and not many know about it.