Very few machines today even have serial ports, and youi often need special drivers to support them. MSCOMM32.DLL is 32 bit, and is emphatically NOT supported by WOW32, even though it can sometimes be coaxed into working anyway.
This can be done, you can get serial communications from today's hardware if you're finicky about what serial port add-on you get and what program or programming language(s) you try to support. It is what my favorite college professor used to call "a non-trivial exercise" to get it working though!
-PatP