Be careful - these aren't the same thing.
So, LoadFrom() usually gives you what you asked for, but not necessarily. LoadFile() is for those who really, really want exactly what is requested. (*However, starting in v2, policy will be applied to both LoadFrom() and LoadFile(), so LoadFile() won't necessarily be exactly what was requested. Also, starting in v2, if an assembly with its identity is in the GAC, the GAC copy will be used instead. Use ReflectionOnlyLoadFrom() to load exactly what you want - but, note that assemblies loaded that way can't be executed.)
LoadFile() has a catch. Since it doesn't use a binding context, its dependencies aren't automatically found in its directory. If they aren't available in the Load context, you would have to subscribe to the AssemblyResolve event in order to bind to them.
So, which one should you use? That depends on which binding context is right for you and whether it matters that the LoadFrom context may redirect the bind. Regarding the latter: