In this work, we correlate the structural properties of DLC films with their photoelectric properties. DLC layers are deposited on silicon wafers by RF plasma-assisted chemical vapor deposition (RF PACVD), The films are irradiated with picosecond Nd3+-YAG laser pulses at different wavelengths (213 and 266 nm) and energies (few mu J to mJ). Photoelectric sensitivity values are reported and compared with those of metals, The DLC coatings are characterized before and after irradiation by IR spectroscopy, micro-Raman spectroscopy and ellipsometry in order to observe laser-induced structural modifications of the layers, In situ measurements of work function variations at the surface induced by laser pulses are also reported.