Time integrated Laser Induced Breakdown Spectroscopy was applied to the study of real samples of polychromes. Two samples respectively from the Spanish Baroque and from the XV century were analysed. The time integrated spectra showed negligible contribution of continuum background emission. The spectra of the Baroque sample indicated the presence of vermilion; this was confirmed by Near Infrared Fourier Transform Spectroscopy. LIBS spectra of the XV century sample showed Ca, Al, Mg, Na and Pb lines and the molecular emissions CN(B-X) and C2(d-a). Relative spectral intensities were measured as a function of the number of laser pulses delivered on the same position of the sample. The LIBS analysis was compared to an exhaustive analytical study.