The photochromic behavior of 2,2-di(4-fluorophenyl)-6-methoxy-2H-1-chromene has been investigated by 19F NMR spectroscopy. Photocoloration under UV irradiation at low temperature led to the formation of three interconverting photoisomers including two merocyanines and an unprecedented allenyl-phenol isomer. Photobleaching with visible light, which was known to lead to reversion to the initial closed chromene, was shown to increase allenyl-phenol concentration. Thermal relaxation of the preirradiated system was also studied at various temperatures. In each case (UV and visible irradiations, thermal isomerization), the kinetics of each of the four species was monitored. Numerical analysis of concentration vs time profiles enabled us to unequivocally establish the global mechanism occurring in each of the experimental conditions and to interpret the specific reactivity of each photoisomer. It has been shown that, among the 12 possible isomerization processes, only some paths were active. For the first time, it has been possible to determine their corresponding thermal activation parameters and photochemical quantum yield ratios.