Until now, black titania has attracted much interest as a potential photocatalyst. In this contribution, we report the first demonstration of the effective strategy to fundamentally improve the photocatalytic performance using a novel sustainable defective titanium-carbon-phosphorous (TCPH) hybrid nanocomposite. The prepared TCPH was used for photocatalytic degradation of the main organic pollutants, which is methyl orange (MO) dye. The physico-chemical properties of as-prepared samples were characterized by various techniques to observe the transformations after carbonization and the interaction between different composite phases. The existence of Ti³⁺ and oxygen vacancies at the surface, and a notable increase in surface area, are all demonstrated by TCPH, together with the distinct core-shell structure. These unique properties exhibit excellent photocatalytic performance due to the boosted charge transport and separation. The highest degradation efficiency of methyl orange (MO) was attained in the case of TCPH when compared with titanium-cellulose-phosphorous (TCeP) and titanium-carbon-phosphorous (TCPN). Accordingly, the highest degradation efficiency was achieved by applying the optimal operational conditions of 1 g/L of TCPH catalyst, 10 mg/L of MO, pH of 7 and the temperature at 25 ± 3°C after 3 min under LED lamp (365 nm) with light intensity 100 mW/cm². The degradation mechanism was investigated, and the trapping tests showed the dominance of hydroxyl radicals in the degradation of MO. TCPH showed high stability under a long period of operation in five consecutive cycles, which renders the highly promising on an industrial scale. The fabrication of highly active defective titanium-carbon-phosphorous opens new opportunities in various areas, including water splitting, and CO₂ reduction.