This paper reports a novel photothermal self-lubricating (PT-SL) anti-icing coating contributing to the structural design of photothermal material and the utilization enhancement of photothermal function. The PT-SL coating was created by the hydrolysis-condensation reaction of tetraethylorthosilicate (TEOS) and γ-methacryloxypropyltrimethoxysilane (MPTMS) on the surface of pre-prepared flower-like CuS particle, followed by crosslinking yielded flower-like CuS@(SiO2-MPTMS) particle with silicone elastomer (Sylgard 184) in the presence of linear poly(dimethyl siloxane) (l-PDMS). The CuS@(SiO2-MPTMS) particle evidenced as black body in the wavelength range 250–2500 nm endowed the PT-SL coating with high photothermal conversion efficiency at a low content due to its flower-like structure with numerous sharp nanoflakes and small pores. The high temperature via photothermal effect could promote the surface migration of liquid-like hydrophobic l-PDMS, bestowing a self-lubricated dewetting property on PT-SL coating. Consequently, the PT-SL coating with a CuS@(SiO2-MPTMS) content of 5 wt% under sunlight was capable of melting and cleaning ice and frost even at a freezing temperature of −25 °C. Under sunlight-free condition, the PT-SL coating also performed low ice adhesion strength ranging from 14.98 to 9.33 kPa and good durability due to the synergism of crosslinked structure, the uniform distribution of CuS@(SiO2-MPTMS) and the surface coverage of liquid-like l-PDMS.