Novel N,C,S-TiO2/WO3/rGO Z scheme photocatalyst was successfully synthesized from graphite, TIOT, and ammonium metatungstate precursors. Material characteristics such as crystal structure, surface morphology, functional groups, specific surface area, elemental composition, band gap energy, and electron-hole recombination were characterized by XRD, TEM, BET, SEM/EDX, FT-IR, UV–VIS, and PL methods. The as-synthesized novel N,C,S-TiO2/WO3/rGO Z-scheme heterojunction photocatalyst exhibited visible light-driven photocatalytic activity (the band gap energy = 2.24 eV), could generate both effective electrons and holes, and presented the lowest electron-hole recombination rate compared to all individual components. Different factors impacting the photocatalytic decomposition of Direct Blue 71 (DB 71) by the N,C,S-TiO2/WO3/rGO system were studied. The results showed that pH of the solution, catalyst load, DB 71 initial concentration, and reaction time affected the DB 71 photocatalytic degradation efficiency. The DB 71 degradation completed after 100 min with a typical efficiency of over 91%, which was much better than other photocatalytic systems. The DB 71 degradation process followed the pseudo-first-order kinetics model with coefficients of determination > 0.95 for all conditions. The photocatalyst was easily regenerated, and exhibited a very good stability, with a photocatalytic degradation efficiency of over 83.0% after 3 cycles.