Intensive efforts have been devoted to develop high-performance light-to-heat converting materials through delicate tuning of solar absorbing materials composition, design of multilayer coating, and engineering of surface structure to achieve high solar absorptance with low thermal emittance and optical reflectance. Here, an overview of materials (metallic and hybrid combination of organic-inorganic and metallic-semiconductor) designs with distinct photothermal conversion mechanisms will be presented. Essentially, these heat generating nanomaterials can be tailored with desirable photothermal actuation and energy generation functionalities through structural engineering and system design. Metamaterial coupled pyroelectric material, that performs synergistic waste heat rejection and photothermal heat-to-electric conversion will also be presented. Unlike any other pyroelectric configuration, this new conceptual design deviates from the conventional by deliberately employing back-reflecting NIR to enable waste heat re-utilization/recuperation to enhance pyroelectric generation, avoiding excessive solar heat uptake and also retaining high visual transparency of the device. Passive solar reflective cooling is realized and in the meanwhile enhanced photothermal pyroelectric performance capitalizing on the back-reflecting effect is validated. Finally, proof-of-concept for concurrent photothermal management and enhanced solar pyroelectric energy generation under a real outdoor environment is demonstrated.