AbstractDesigning stable, low‐cost yet highly active electrocatalysts is crucial for overall water splitting, representing a promising approach for clean energy generation. In this work, periodic density functional theory calculations are applied to investigate, for the first time, the possibility of activating the inert basal surfaces of 2H‐MoTe2 monolayers by N‐ or P‐doping for overall electrocatalytic water splitting. The results show that both N‐ and P‐doping significantly change the surface charge distribution and electronic band structure of 2H‐MoTe2. In addition, the doping‐induced structural disorder generates more active sites, leading to improved electrochemical activities for both hydrogen and oxygen evolution reactions (HER and OER). Especially, N‐doped 2H‐MoTe2 (4 × 4 × 1) exhibits a better OER catalytic performance with a small overpotential of 1.82 eV (vs normal hydrogen electrode), while both N‐ and P‐doped MoTe2 monolayers exhibit outstanding HER catalytic performance with a Gibbs free energy of the hydrogen adsorption ( for N‐doped MoTe2 and for P‐doped MoTe2) smaller than that of pristine 2H‐MoTe2 (). The study provides an effective strategy for regulating the electroactivity of layered transition metal dichalcogenides for enhanced overall water splitting.