The development of electrocatalyst with remarkable activity for hydrogen production through water or urea splitting is critical for coping with the energy crisis, but still remains a lot of obstacles. In order to improve the electrocatalytic activity, rational design of nanostructures with rich active sites is an efficient method. Herein, a porous flower-like Mo-doped NiS on Ti mesh (Mo-doped p-NiS/Ti) is synthesized through selective etching of Al(OH)(3) in Mo-doped NiAl layered double hydroxides, and then followed by a facile hydrothermal sulfuration process using sodium sulfide as S source to afford Mo-doped p-NiS/Ti. As a non-noble metal catalyst, Mo-doped p-NiS/Ti catalyst exhibits excellent electrocatalytic performance in electrolyte of 1.0 M KOH or 1.0 M KOH with 0.3 M urea. To drive a current density of 10 mA.cm(,)(-2) a small overpotentials of 147.6 mV and 162.3 mV in 1.0 M KOH and 1.0 M KOH with 0.3 M urea are required, respectively, and remarkable durability is observed in 1.0 M KOH or urea water solutions. More significantly, Mo-doped p-NiS/Ti holds promises for potential implementation in the overall water or urea splitting.