Utilizing pluronic P123 and MoO42− as morphology directing reagents, the ternary NiFeMoS anemones-like nanorods with scaly surface supported on nickel foam (NiFeMoS/NF-P) have been synthesized through a two-step method. Firstly, Ni-Fe hydroxides film has been electrodeposited on the surface of NF, leading to a homogeneous doping of NiFe. Then, the anemones-like nanorods with scaly surface have been prepared though a facile hydrothermal sulfuration with co-adding of P123 and MoO42−. SEM and TEM images confirm the NiFeMoS/NF-P has anemones-like nanorods morphology with scale-like surface composed of many nanosheets. With the absence of P123 or MoO42−, scaly surface of NiFeMoS nanorods can’t be obtained, implying the role of P123 and MoO42− as organic-inorganic hybrids directing reagents. The detailed influence of P123 and MoO42− on NiFeMoS nanostructure and electrocatalytic activity for water splitting has been investigated. NiFeMoS/NF-P as bifunctional electrocatalyst exhibit excellent electrocatalytic performance in 1M KOH, producing a current density of 150mAcm−2 at a overpotential of 280mV for OER and a overpotential of 100mV at 10mAcm−2 for HER. Moreover, in the same system for overall water-splitting, NiFeMoS/NF-P present remarkable performance with a current density of 100mAcm−2 at a low cell voltage of 1.52V.