Yes, but it was extremely rare, depending on what you consider "radioactive".

A form of Uranium known as Pitchblende or Uraninite was used dating back to the early Roman empire to color ceramics and later glass. It was not known at the time to be harmful. It's important to understand that naturally occurring radioactive ores are usually very weakly radioactive (long half lives or occur as a small percentage of the overall ore's composition), since stronger radioactive reactions would have decayed by the time humans came into contact with them. Enriching the radioactive elements enough to produce damaging results would take modern technology.

I'm not entirely sure about whether other "popular" radioactive elements like Uranium/Thorium etc. were found in a large enough amount to be considered sound industrial investments. I'm not much of a geologist I'm afraid.