Sure you can. In the past, I've usually sandblasted and epoxy-primed the insides of rims. I'll agree with glennster on the POR15 though. I started using it last year for the inside of rims and have been very impressed with it.
I have never brushed a paint that flowed out as well as POR15. It's indeed very hard and slick. After initially seating the beads on a 16.9x26 tractor rear (lightly lubricated beads), as soon as I let the air out to re-air to the proper pressure, both beads slipped completely back and had to be reseated again. That's not a problem but I never observed that happening before. I have not had any problem with the tire slipping around on the rim, even during hard use while spinning (with chains) in packed gravel or turf. The issue many may be unaware of is that it's a moisture-cured urethane product. As such, it has isocyanates in it even though it is not a two-part paint. Also, if there is even a small remnant of paint in the rim contact area of the cover, you'll have to destroy the can to get it apart next time. Following all the instructions with this stuff is extremely important.
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