Low density polyethylene (LDPE) and polypropylene (PP) exhibit a photoluminescence (PL) band, which emits photons with an energy of around 4.3 eV when excited by photons with energies around 6.4 eV. The origin of this PL band has been assigned to α, β-unsaturated carbonyl. In this paper, the appearance of PL was examined for four kinds of polyolefin and four kinds of biodegradable polymers. As a result, it has become clear that all the polymers show a PL band with a PL excitation spectrum and a PL spectrum similar to those of the above-mentioned PL band in LDPE and PP. The decay profiles observed for these PL bands indicate that they are fluorescence. Furthermore, the intensity of the PL becomes weak for all the four polyolefin samples and the polylatic acid sample if ultraviolet photons were irradiated to the sample. Quantum chemical calculations carried out by assuming a model of α, β-unsaturated carbonyl have revealed that the PL originates in the π* to π transition of electrons in the carbon-carbon double bond.