Among the various fire‐retardants (FRs) known, phosphorus is vital to the development of effective FRs due to its flexibility. Additionally, the additives and combinations of phosphorus with various multicomponent moieties (e. g. P−Si, P−P, P−B, etc.) can serve the purpose in different phases to improve flame retardance properties. With an increased cognizance of recyclable, eco‐friendly, and bio‐based materials, phosphine oxide‐based materials/coatings can fulfill the criteria for flawless and future FRs. In this regard, the present review highlights the most promising organophosphorus‐based compositions as non‐intrusive FRs. The classification, synthetic methods, related mechanisms, and high‐end FR applications of various recently developed organophosphorus‐based molecules and materials are demonstrated. Among various organophosphorus compounds, the phosphorus‐based polyurethane materials display remarkable FR properties and non‐toxic behavior. Notably, the flame retardance of the epoxy resins is enhanced significantly with the presence of more P=O bonds and amino groups. The limitations and advantages of organophosphorus‐based materials are compared with the traditional FRs. Also, the challenges persisting in improving current flame‐retardant materials need to be addressed. However, the success of these materials and treatment methods strongly depends on the ability to impart desired functionality, durability, and scalability without compromising environmental problems.