As the utilizing of porphyrins and metalloporphyrins in high dose dosimetry becomes more prevalent, research on structural effects of these molecules on dosimetric characteristics and physicochemical properties of their film dosimeters becomes more and more essential. The present study emphasizes dosimetry (measuring radiolytic bleaching of two novel film dosimeters with spectrophotometric methods against 60Co γ-rays exposure in dose range of 0–100 kGy) and evaluating substituent effects on the radiation response of the film dosimeters (role of organic groups and changing the metal core of porphyrins). With casting of solutions of polycarbonate (PC) containing 0.5 wt.% 5,10,15,20-Tetrakis(2,4,6-trimethoxyphenyl) porphyrin (TTMPP) and 5,10,15,20-Tetraphenyl-21H,23H-porphine manganese (III) chloride (Mn-TPP), two novel radiochromic films with the thickness of 20 μm were fabricated. The presence of porphyrin fragments has been observed in the UV–Vis spectra after γ radiation. Due to the changes of the metal core and substituents of the dye ring, meaningful shifts of maximum absorbance of Soret bands of porphyrins and different radiation response of film-dosimeters were observed. The results were compared with the other polycarbonate/porphyrin film dosimeters. The results indicate that the radiation-induced decoloration of PC/Porphyrin films can be reliably tuned and used in high dose dosimetry.