Here's a breakdown:
* It's the word you're looking up. For example, if you're looking for the definition of "cat," "cat" would be the headword.
* It's usually the most important word in the entry. The definition and other information in the entry relate to the headword.
* It's often followed by pronunciation information. This can be phonetic symbols or a pronunciation guide.
* It can be a noun, verb, adjective, adverb, etc. Dictionaries are organized alphabetically by headword.
Essentially, the headword is the "star" of the dictionary entry, and everything else revolves around it.