Anionic substitution is an effective approach to optimize the catalytic activity of Mo based transition metal dichalcogenide (TMD)- MoS2 towards hydrogen evolution reaction (HER). By optimizing the S-to-Se ratio, materials with the ideal Gibbs free energy of hydrogen adsorption (ΔGH) values are synthesized (MoS2, MoS1.4Se0.6, MoS1.2Se0.8, MoSSe, MoSe2) and their HER performance is examined in 0.5 M H2SO4 solution. Density functional theory calculations of hydrogen adsorption energy on the surface of the electrocatalysts show that Se substitution facilitates electron transfer between the catalyst surface and the hydrogen donor, thereby lowering the additional potential required for water splitting, making MoS1.2Se0.8 the most favorable HER electrocatalyst with the lowest value of adsorption energy. Further enhancement in the electrocatalytic activity of mixed anion TMDs has been achieved by the incorporation of carbon nanotubes (CNTs). MoS1.2Se0.8-CNT nanocomposite exhibits superior HER performance with an overpotential of 118 mV and a Tafel slope of 63 mV/decade as compared to MoS1.2Se0.8 sample owing to the synergetic effect from CNTs and MoS1.2Se0.8.