Steady-state and time-resolved photoluminescence (PL) spectra of natural and synthetic melanin, as well as melanin composites with surfactant, sodium dodecylbenzenesulfonate, and polymethine dye, astraphloxin, have been studied. The melanin molecules having differently charged peripheral groups with terminal O atoms and OH groups mixed with the negatively charged surfactant or positively charged astraphloxin dye feature new PL spectral bands. The kinetics of PL and time-resolved emission spectra for the melanin and the composites were also investigated and discussed in terms of intermolecular complexation, nano-aggregation and formation of charge-transfer states. The studies are aiming to understand the electronic properties of various melanins, particularly natural ones.