The charge separation and transfer are the major issues dominating the under-laying energy conversion mechanism for photocatalytic system. Construction of semiconductor-based heterojunction system considered to be viable option for boosting the spatial charge separation and transfer in the photocatalytic water splitting system. Here, we design a ternary heterojunction of Ti₃C₂/N, S-TiO₂/g-C₃N₄ by thermal annealing and ultrasonic assisted impregnation method having a well-designed n-n heterojunction and noble metal free Schottky junction for adequate hydrogen evolution. The optimal content of 4 wt% Ti₃C₂ on N, S-TiO₂/g-C₃N₄ (4-TC/NST/CN) exhibit the highest rate of hydrogen generation 495.06$\mu$ mol h⁻¹ which is 3.1, 4.1 and 1.6 fold higher than the pristine N, S doped-TiO₂, g-C₃N₄ and binary hybrid (N, S doped-TiO₂/g-C₃N₄) respectively, with 7% apparent conversion efficiency (ACE). The increment in the activity is described to the robust photogenerated carrier separation and double charge transfer channels because of the formation of dual heterojunction (n-n heterojunction and Schottky junction). XRD and Raman results revealed the occupancy of Ti₃C₂ in the heterojunction due to the strong interaction between Ti₃C_2, with N, S doped-TiO₂ and g-C₃N₄. The HRTEM analysis confirmed the formation of close interfacial junction between the Ti₃C₂, N, S doped-TiO₂ and g-C₃N₄. Moreover, the higher photocurrent, low PL intensity and lower impedance arc suggested the lower charge carrier recombination rate in 4-TC/NST/CN heterojunction. This work represents a significant development to establish a sound foundation for future design of MXene-based ternary hybrid system towards significant charge carrier separation and transfer for H₂ production activity.