Organisms with active camouflage ability exhibit changeable appearance with the switching of environments. However, manmade active camouflage systems heavily rely on integrating electronic devices, which encounters problems including a complex structure, poor usability, and high cost . In the current work, we report active camouflage as an intrinsic function of materials by proposing self-adaptive photochromism (SAP). The SAP materials were fabricated using donor-acceptor Stenhouse adducts (DASAs) as the negative photochromic phases and organic dyes as the fixed phases (nonphotochromic). Incident light with a specific wavelength induces linear -to- cyclic isomerization of DASAs, which generates an absorption gap at the wavelength and accordingly switches the color. The SAP materials are in the primary black state under dark and spontaneously switch to another color upon triggering by transmitted and reflected light in the background. SAP films and coatings were fabricated by incorporating polycaprolactone and are applicable to a wide variety of surfaces.