Two laser cleaning approaches based on ablation by ultraviolet laser pulses of femtosecond (fs) and nanosecond (ns) durations for the removal of shellac varnish from egg-yolk based tempera paints are investigated. Laser irradiation effects, induced on the varnish layer and on the underlying temperas by multiple pulses in the fs domain at 398 and 265 nm and single pulses in the ns domain at 213 nm, were examined following a spectroanalytical approach. By using optical microscopy, colorimetry and laser induced fluorescence it was found that irradiation of the varnished temperas with fs pulses changes the texture of the varnish surface and results in degradation of the underlying coloured paint. In contrast, operating with pulses of 15 ns at the highly absorbed wavelength of 213 nm, controlled micrometric layer removal of the varnish is possible without noticeable modification of the coloured temperas. These results widen the choice of laser conditions for painting restoration.