Two types of melanin films: self-arranged ordered films and amorphous films have been studied in the present paper. The structure, absorption spectra, spectra of photovoltage, and spectra of time-resolved photoluminescence have been investigated for both types of melanin films. Time-resolved photoluminescence was measured at room temperature at different delay times. The reason for the difference in the electronic properties of structurized and amorphous films of melanin is attributed to the structural features of the films related to ordered dendrite-like structures and amorphous disordered ones, respectively.