the first series is always the line and the rest are bars. you control it using sorting.
Also note that you can set the number of lines (or symbols) that will appear in the chart. Go to chart properties > General and you'll see the open field that shows Number of Lines (or Symbols). If you have four series in your chart and you want two lines, then put 2 in the box, and place these two series first and second in your chart builder.
This makes it much easier to manage secondary axes where you may have % and a large number on the other axis.
@Wheelzzz, did Godzilla's reply help answer your question?
Yes it did! Thanks all!
This does not seem to be the case anymore and it appears the line is being arbitrarily chosen. In fact, the line gets changed when I add a data label (what ?!?!)
Specifically, I have a series that is a count of certain string types so sorting does not work. Is there anyway to choose which category is the line in this instance?