A novel TiC-TiN/Al2O3 tandem solar selective absorbing coating was successfully deposited on Si (1 0 0) and stainless steel (SS) substrates by reactive RF magnetron sputtering deposition. The spectral characteristics, microstructure, thermal stability and solar-thermal conversion efficiency of the coating before and after a long annealing in vacuum were investigated systematically. The optical constants of the coating are measured by an Ultraviolet–visible-near-infrared (UV/Vis/NIR) spectrometer, and the chemical composition analysis, structure information and surface morphology are investigated using XRD, XPS and FESEM. An excellent absorptance (α = 0.92) and a low emittance (ε = 0.11) at 82 °C are obtained by the as-prepared coatings. After annealed at 500 °C for 100 h in vacuum, there is no significant change in micromorphology and optical properties of the coating, which produces a good solar-thermal conversion efficiency. These results indicate that it can be applied as a potential coating material to a high temperature concentrated solar power (CSP) system.