We have two rectangular skylights in a vaulted ceiling. Both need new tinted window film. I have considered doing this myself, but really would prefer to hire it out. The problem is I have no idea who would do this type of work.

As for doing it myself, they are about 14' up and angled about 30 degrees, just estimating. I really do not want to rent scaffolding to do this. The existing film is bubbling off.

Anyone ever deal with this?

I would look at getting a shade for the skylight.
In the winter time you need the heat while in the summer it needs to be blocked off.

Can the window itself be removed from the outside / roof?

Tinting, itself, is pretty easy, but 14ft up and at a wonky angle would be a pain.

If doing it myself, and the window was removable from the outside, I'd grab a ladder, pull the window, tint it on a flat surface on the ground, and reinstall the window afterwards.

Otherwise, scaffolding or a 3rd Party sound like your best option.

It's easy to do is the window is accessible. Did a couple myself with a kit from Home Depot.

We priced the work from a company we met at a home improvement show. They use the 3M brand of tint that also provides a shatter resistant property. Not proof, but prevents or eliminates shards should some dufus or hail storm decides to visit.

Like many of these projects it looks easy but there are tricks the pros use. The pros also come with scaffolding and know how to put it up and then take it down.