Yes, I have stopped mine from starting on start-up.

Goto options, go to the advanced tab, (very bottom) select system start up (very bottom again) and uncheck the box "Run on System start up". This way the program will not start until you double click on the limewire icon.

The option under conncections only affects conncecting to the network when LW is started. I believe it benefecial to leave this box checked.

Alan