If you develop applications at your company and another group there uses it to do the actual business of the company, have you actually seen how they use the software? Seems a bit crazy, right? You developed it, so of course you know how it works! Not quite so. The people who use your applications all day every day at work will find little nuances about it that you never would have dreamed of. They'll take six clicks to get something done when you thought it only would take two.
You won't really know how they use it until you sit with them and watch them for a few minutes. Requesting this to your boss should show that you care enough about the business to help out the productivity of the users and the quality of the software you give to them. To get an even better idea is to see if you can actually do a little bit of what they do to get the full effect. Then take notes...anything that comes to mind. How do you think this can be improved? What issues were you having to accomplish a certain task? Were there any performance problems that had you waiting for a task to complete? Could something be done simpler to minimize the user (in this case, you) from having to think about what should be done on the page?
I actually propose the whole team to do this. Then once everyone has finished, compare notes and even have a small meeting on all the things that can be improved.
I just did this today and saw massive productivity improvements and you can bet I'll share them with the team as soon as I review my notes.