With the increasing development of photothermal techniques in various fields, particularly concentrated solar power (CSP) systems and solar thermoelectric generators (STEGs), the demand for high-performance spectrally selective absorbers (SSAs) has grown significantly. These SSAs are essential in achieving high solar absorption and minimal infrared thermal loss, thereby significantly enhancing solar utilization efficiency. This need becomes particularly critical in CSP systems, where high temperatures are pivotal for improved efficiency. However, the necessity for high temperatures imposes stringent requirements on the fabrication of SSAs, given the inherent trade-off between optical performance and thermal stability. SSAs typically require nanoscale thin films, but they are prone to oxidation and diffusion at high temperatures. Recent developments in photothermal materials, including ceramic composites, MXenes, high-entropy materials, and graphene, offer promising solutions to enhance SSAs’ performance. This review article provides a comprehensive evaluation of the latest advancements in these emerging photothermal materials. We summarize the strategies for integrating these advanced materials with already established nanostructures, which is a highly promising approach for the development of advanced SSAs. Additionally, the review explores the application of SSAs in CSP systems and STEGs to boost power generation efficiency. We conclude by summarizing the challenges and opportunities in the field of high-temperature SSAs, offering valuable insights into the development of high-performance SSAs and their role in solar-thermal power generation systems