I suppose it could work. Often I look at home made solutions against what I find in the RV market that already exists and usually find there is a good reason why the manufactured items are designed the way they are. In the case of skylights, they are usually a dome type to obviously shed water. I have used acylic before on other applications and it's difficult to drill into without cracking it thus inviting problems. I am not sure how it would fare with the constant moving, flexing, expansion and contraction, and vibrations that it would experience on an RV.
2013 ACE 29.2