The stainless steel chemical coloration demonstrates excellent repeatability of process when adopted to fabricate solar selective absorber coatings (SSACs) on TTS445J1 stainless steel base material. The optical performance, morphology, and composition of coatings are characterized by UV-3600, IR-Affinity-1, SEM, EDS, etc. The experimental results suggest that the Cr-Fe composite oxides with coatings in a spinel structure obtained by chemical coloration on a stainless steel surface exhibit outstanding spectral selectivity, with α/ε = 0.9334/0.1326. The coatings were generated by the direct reaction between the stainless steel substrate composition and the coloring solution, which changes the traditional way of combining the coating with the substrate by physical methods. Comparing the SEM images of the coatings before and after aging at 500 °C in air, we noticed no significant changes at the interface between the coatings and the substrate, indicating excellent coating adhesion. At the same time, the substrate grains did not change much after the chemical reaction of the stainless steel substrate, indicating that the oxidation resistance of the stainless steel substrate was not weakened. Finally, the Cr-Fe composite oxide exhibited excellent thermal stability in air. Based upon a microstructure analysis, the Performance Creation (PC) is 0.01 after aging at 500 °C for 200 h in high-temperature air, primarily because of the loss of H2O molecules from the hydrates in the coatings. After aging for 800 h, PC = 0.0458. After the aging hours are extended to 1000 h, PC = 0.0762. During the aging process at high temperature, the coatings of the Cr-Fe composite oxides maintained stable composition and phase structures. The decay in optical performance is due mainly to the reconstruction of the surface morphology of the coatings as a result of the largening of grains.