Pristine thermally evaporated nickel-(II)-tetraphenyl-21H,23H-porphyrin (NiTPP) thin films are amorphous, but after 4 and 8 h of UV illumination, the films become crystalline with preferred orientations of ( 112), ( 103) and ( 004) and crystallite sizes of (13, 18, 16) and (42, 31, 38) nm after 4 and 8 h, respectively. After UV illumination for 4 and 8 h, the NiTPP thin films are characterized by blueshifted absorption coefficients, increasing the optical and fundamental gap values and decreasing the dispersion parameter values. The dielectric properties display energy storage regions corresponding to the peak values of optical conductivity, which provides an elegant confirmation of the tailoring and tuning of band gaps, energy storage properties and optical conductivity by UV illumination time. Therefore, NiTPP films may be good candidates for environmental and energy storage applications.