The structure of the Langmuir film of an amphiphilic spiropyran, 1',3'-dihydro-3',3'-dimethyl-6-nitro-1'-octadecyl-8-(docosanoyloxyme thyl)spiro[2H-1-benzopyran-2,2'-(2H)-indole] (SP), is investigated using Brewster angle microscopy (BAM). The BAM observations show that the Langmuir film of SP can be roughly categorized into three regimes: a low-temperature regime at 7-13 degreesC a medium-temperature regime at 23-30 degreesC; a high-temperature regime at 40 degreesC. The low-temperature regime is characterized both by the domains that are formed just after the spreading and by the onset of the surface pressure when the domains are merged together to form continuous trilayers. In the medium-temperature regime, a continuous monolayer film is formed after the solvent evaporation, followed by the growth of "embryos" with compression. Around the phase transition point, the "embryos" serve as the "nucleation sites" of the circular trilayer domains. The characteristic features of the high-temperature regime are similar to the ones of the medium-temperature regime except for the absence of a steep rise in surface pressure after the plateau region and the absence of the circular trilayer domains. UV illumination of the Langmuir films leads to the isomerization of SP into merocyanine (MC). However, J-aggregates of MC are formed only when the circular trilayer domains are present. On the basis of the above results, we present a phase diagram of the Langmuir film of SP. The structure and photoreaction depend strongly on the phase of the Langmuir film, indicating that the area/molecule is not the only decisive parameter.