A study of thermal, structural, electrical and optical characteristics of molybdenum black surface coatings on various substrates has been made. The suitability of these coatings for use as selective absorbers for solar collector applications has been assessed. Molybdenum black (Mo black) coatings were prepared by electrodeposition (on aluminium) and a chemcial conversion method (on zinc and electroplated cobalt on nickel plated copper substrates). The solar absorptancer (αs) and thermal emittances (εth) of the coatings were determined from room temperature spectral reflectance measurements in the solar (0.3 to 2.5μm) and infrared regions (2.5 to 50 μm) respectively. The effect of different preparation parameters and substrate pretreatments on the spectral selectivity has been investigated in order to optimize the thermal performance. The spectral selectivity is related to the Mo-black coating thickness and surface roughness together with the microstructure, of the substrate and the intermediate layer. Dip coatings on polished zinc have significant selectivity (αs/ εth = 8.4 when αs = 0.76). The absorptance of the dip coatings is increased to 0.87 with εth = 0.13 by chemical etching of zinc prior to coating deposition. For coatings on electroplated cobalt on nickel plated copper (cobalt (NC) substrate), an absorptance as high as 0.94 has been obtained with an emittance value 0.3. By using an addition agent in the plating solution of cobalt the high emittance can be reduced to 0.1 with αs = 0.91 giving a coating with a relatively high efficiency (82.5%) for photo-thermal energy conversion. A study of the surface composition and microstructure of the coatings has been made using scanning and transmission electron microscopy together with electron diffraction, X-ray diffraction and X-ray photoelectron spectroscopy. The structural investigations indicate that Mo-black coatings contain polycrystals of orthorhombic Mo4O11 with a small proportion of Ni(OH)2. Presence of water and also Mo4O11 in the coatings are evident from IR spectroscopy study. The bandgap of the coating has been determined from optical transmission spectra (1.66 eV) and also from reflectance spectra (0.85 eV). The discrepancy between these two values has been discussed. The refractive indices of the coatings have also been estimated. The band gaps and refractive indices are found to be related to the spectral selectivity of the coatings. The durability test of the coatings shows that the coatings on etched zinc are more resistant to heat treatment than the coatings on unetched zinc. The coatings on cobalt (NC) substrates also show good stability for relatively short periods at temperatures ~400ºC. A study of the electrical properties of Mo-black coatings suggests that at electrical field strengths (greater than 106v/m the dominant conduction process is of the Poole-Frenkel type. The activation energy of the conduction process has been estimated to be -0.56 eV at higher temperatures. The effect of heat treatment on the electrical properties of the coatings has been examined. The dielectric constant of Mo-black has been estimated from A. C. measurements. At high frequency (20 kHz) the value of the dielectric constant is about 4.0.