Analysis by laser-induced breakdown spectroscopy (LIBS) is compared, on the basis of a hybrid experimental set-up, with laser ablation time-of-flight mass spectrometry (LA-TOF-MS) for the characterization of materials relevant to cultural heritage. The present study focuses on the analysis of selected paint materials such as lithopone, a white inorganic pigment, and two synthetic organic paint formulations, lemon yellow and phthalocyanine blue. Optical emission spectra, obtained by LIBS, lead to rapid, straightforward identification of the elemental content of the paint samples while mass spectra yield, additionally to elemental analysis, complementary isotopic analysis and, more importantly, enable detection of molecules and molecular fragments, permitting a more complete structural and compositional characterization of composite materials. Mass spectra were recorded either simultaneously with the optical emission ones, or sequentially. The latter was preferred for materials having significantly lower fluence threshold for desorption/ionization relative to plasma formation resulting to optimum mass resolution and minimal surface damage. In all, the results of this study demonstrate the advantages of instrumentally complementing LIBS with TOF-MS in relation to applications in cultural heritage materials analysis, with exciting prospects when laser ablation sampling can be carried out under ambient atmosphere.