A simple solution method is used to synthesize NiCo2O4, NiCo2O4/C and NiCo2O4/Ti4O7. NiCo2O4/Ti4O7 displays the highest catalytic activity and best stability for OER. Ti4O7 enhances the conductivity and the amounts of Co2+ and Ni3+ of NiCo2O4. The increased amounts of active centers contribute to the good catalytic activity. NiCo2O4/Ti4O7 is a promising anode electrocatalyst for water electrolysis.