Orotic acid is a natural heterocyclic compound that acts as a nucleation agent in poly(lactic acid) (PLA). PLA materials with increasing orotic acid content were prepared and characterized. It was found that crystallinity of about 28% was reached with 0.3% content of the agent. Further enhancement in the content of the agent did not provoke any additional significant increase of crystallinity. Subsequently, it was investigated whether the orotic acid content affected photodegradation of PLA and, in the next phase, its biodegradation. The results of rheological measurements showed that the compound slightly accelerates photodegradation of the material, which was accompanied by the cleavage of PLA chains. Previous photodegradation was shown to accelerate the subsequent biodegradation by shortening the lag phase of the process, where the explanation is probably in the reduction of the polymer molecular weight during the photodegradation. Moreover, the presence of orotic acid in both initial and photodegraded samples was found to influence biodegradation positively by shortening the lag phase and increasing the observed maximal rate of the biodegradation.