Apart from the fact that unlink is unix-specific (as pointed out by Chris), we read in the POSIX manual:
If path does not name a directory, remove(path) is equivalent to unlink(path).
If path names a directory, remove(path) is equivalent to rmdir(path).
As for the directory-passed unlink, we read:
The path argument must not name a directory unless the process has appropriate privileges and the implementation supports using unlink() on directories. (…) Applications should use rmdir() to remove a directory.