This work aimed to develop a phosphorous-based biorefinery process for obtaining phosphorylated lignocellulosic fractions in a one-pot protocol from coconut fiber. Natural coconut fiber (NCF) was mixed with 85 % m/m H₃PO₄ at 70 °C for 1 h to yield the modified coconut fiber (MCF), aqueous phase (AP), and coconut fiber lignin (CFL). MCF was characterized by its TAPPI, FTIR, SEM, EDX, TGA, WCA, and P content. AP was characterized regarding its pH, conductivity, glucose, furfural, HMF, total sugars and ASL contents. CFL structure was evaluated by FTIR, ¹H, ³¹P and ¹H-¹³C HSQC NMR, TGA and P content and was compared to that of milled wood lignin (MWL). It was observed that MCF and CFL were phosphorylated during the pulping (0.54 and 0.23 % wt., respectively), while AP has shown high sugar levels, low inhibitor content, and some remaining phosphorous. The phosphorylation of MCF and CFL also showed an enhancement of their thermal and thermo-oxidative properties. The results show that a platform of functional materials such as biosorbents, biofuels, flame retardants, and biocomposites can be created through an eco-friendly, simple, fast, and novel biorefinery process.