The photochemical reaction processes, i.e., photo-dissociation of a reaction solution, defluorination of fluorocarbon [FEP], and substitution of a hydrophilic group, were measured in real time, when irradiating a Xe2 excimer lamplight on the water or ammonia solution as a reaction solution and FEP placed on the attenuated total reflectance [ATR] prism. In case of ammonia solution, with the increase in irradiation time, the absorption peaks of 3300 cm−1 and 1650 cm−1 gradually decreased, and the new absorption of -CF2-NH2 gradually appeared at 1410 cm−1, which presented the strongest absorption after UV irradiation for 25 minutes. The results indicate that the ammonia water has turned to amino groups. In addition, the contact angle of water was measured. When compared to the untreated sample, whose contact angle was 110 degrees, the contact angle of the sample treated with water became 31 degrees after the Xe2 lamp irradiation for 25 minutes, and that of the sample modified by ammonia water further improved to 27 degrees after the irradiation for 25 minutes.