Chemiluminescence (CL) reactions have been widely employed and explored over the past 50 years because they offer unique light emission upon a defined chemical stimulus. In this Minireview, we focus on peroxyoxalate (PO) compounds because they feature very high quantum yields tuneable over the entire visible spectrum, allowing for visible‐light detection by the naked eye without the necessity for expensive analytical instruments. Although analytical methods have been extensively described, PO‐CL read‐out is a strongly emerging field with ample industrial potential. The state‐of‐the‐art PO‐CL detection read‐out systems for various key analytes is here explored. In particular, structural requirements, recent developments of PO‐CL read‐out probes and current limitations of selected examples are detailed. Furthermore, innovative approaches and synthetic routes to push the boundaries of PO‐CL reactions into biological systems are highlighted. Underpinned by recent contributions, we share perspectives on embedding PO‐CL molecules into polymeric materials, which they consider the next step in designing high performance solid‐phase read‐out systems.