Polymer optical fibers (POFs) have been utilized in several applications since the late 1950s. Adding photoluminescence (PL) to the fiber considerably widens the optical functionality of POFs and opens new application fields. In recent years, the availability of laboratory-scale production methods with industrialization potential has triggered a surge of new studies and developments in the promising area of PL-POFs. These applications, profiting from the addition of PL to fibers, are identified in this review as: light harvesting, sensing, color illumination, anti-counterfeiting, and random lasing. Progress in these fields is foreseen to generate a need for larger quantities of fibers, therefore large-scale manufacturing and processing methods are becoming more relevant. This review thus provides an overview of the most important developments in this emerging area, together with a description of the key parameters describing PL-POF performance and efficiency.