The accumulation of ice may cause serious safety problems in numerous fields. A photothermal superhydrophobic surface is considered to be useful for preventing ice formation because of its environmentally friendly, energy-saving, and excellent anti-icing/de-icing properties. However, it easily fails to work in the absence of sunlight. To improve its anti-icing property without sunlight irradiation, a multifunctional photothermal phase-change superhydrophobic film (MPPSF) consisting of phase-change microcapsules (PCMs) and carbon nanotubes (CNTs) was fabricated using a facile spraying method. Benefitting from the excellent light-thermal conversion effect of CNTs, the surface temperature could increase from -20 to 130.1 °C within 180 s under 808 nm near-infrared laser irradiation of 1 W/cm2, thus realizing high-efficiency de-icing. Meanwhile, a portion of the light-thermal energy was stored in the MPPSF because of the phase change of the PCMs. Without sunlight irradiation, the latent heat of the PCMs was released when the external temperature approached the phase-transition temperature. The synergistic effects of the phase-transition latent heat release and superhydrophobicity allowed the MPPSF to effectively hinder the formation of ice for 10.1 min at -20 °C. Therefore, this MPPSF with outstanding anti-icing and de-icing performances is expected to achieve ice prevention and removal in all-days.