The removal process of degraded superficial layers from marble samples by Nd:YAG lasers was studied while simulating operative conditions of stone artwork restoration. The effects of laser irradiation at 1064 nm with three different pulse durations of 6 ns, 20 µs, and 200 µs were investigated by time-resolved shadowgraphy and emission spectroscopy of the ejection plume to characterize the specific interaction regimes, with particular concern given to the occurrence of side effects, such as thermal and mechanical damages to the substrate, that could affect the laser cleaning procedure.