Of course Word can create a TOC for the contents of the current doc. (Geez, @squidcake… where do you think many PDFs come from?)
It involves the use of heading styles and section numbers in your doc when you’re writing it in the first place.
If you’re using Word 2007, go to the References tab and look for the Table of Contents button on the ribbon. You can get all kinds of fancy by choosing how detailed you want to get with listing the various levels of sub-headers, custom styles, and whatnot.
Your best bet would probably be to open up the Help facility in Word (just hit F1) and search for “Table of Contents”. All the gory details will be laid out right in front of you.