Not much point in declaring the argument type if only NULL is permitted. Just declare it IntPtr and pass IntPtr.Zero.
The debugger is pointing out that you forgot to declare the CallingConvention. It is not the default for .NET, this is a __cdecl function. So the proper declaration would be:
[DllImport("libvlc", EntryPoint = "libvlc_new",
CallingConvention = CallingConvention.Cdecl)]
public static extern IntPtr New(int argc, IntPtr argv);
Called as:
New(0, IntPtr.Zero);
Do try to pick a better name...