High-entropy borides (HEBs), as a category of high-entropy materials, exhibit remarkable thermal stability, a broad compositional range, and finely tuned electronic structures, leading to an excellent functional performance. Despite these advantages, their application in photothermal materials has rarely been reported. Herein, we employ a HEB target with multiple transition-metal elements to develop solar selective absorption coatings (SSACs) with simple and scalable bilayer structures for photothermal applications. The performance of these coatings is enhanced by designing different antireflective layers. The designed SSACs, both stainless steel (SS)/HEB/Al₂O₃ and SS/HEB/Si₃N₄, exhibit high absorptivity and low thermal emittance (α/ε = 90.0%/8.6% and 91.6%/8.6% at 82 °C). Thermal stability tests show that the absorbers could withstand annealing at 500 °C for 5 h, while maintaining a good optical performance. Long-term thermal stability tests indicate that the coatings retained good spectral selectivity after annealing at 400 °C for 100 h. Notably, the coatings demonstrate advanced photothermal conversion efficiencies of 88.3% and 89.9%, respectively, at 400 °C under 100 sun. In practical simulated solar irradiation experiments, the absorber achieves temperatures of about 85 °C under 1 sun, surpassing the performance of commercial nonselective absorbing coatings. Additionally, the absorbers maintained a stable photothermal performance through six on–off cycle experiments. In summary, the designed SSACs based on HEBs exhibit excellent optical properties and efficient photothermal conversion at moderate temperatures. This study highlights the significant benefits and potential advancements in solar energy collection offered by HEB-based SSACs.