LO Writer 6 User Guide, chapter 18 covers the use of interactive forms, but doesn’t describe all the features. “Notable omissions are using forms in HTML documents and writing macros to link to form controls.”
That being said, a drop-down list takes its range of entries from a database. So you have to create a database (File > New > Database). It may be that the range of designs offered by the wizard includes just the one you need. Otherwise you’ll have to specify the database fields from scratch, as well as inserting the data into each entry.
The database needs to be registered in your LO list of available databases. And when you create your list box (with Form > Design Mode checked, click on Form > List Box) you must also say in the dialog which database the box takes its data from.
It seems a bit heavy-handed to have to use a database for this, but I don’t know of a simpler way — e.g. to embed the options directly into your document. But chapter 18 of the Guide gives fairly full instructions. And if that’s not enough, there’s the Base Guide to read as well, available from the same help page as the Writer Guide above.