Purposely changing the rate-determining step (RDS) of oxygen evolution reaction (OER) remains a major challenge for enhancing the energy efficiency of electrochemical splitting of water. Here we show that the OER RDS can be regulated by simply varying the cation and anion complexity in a family of the metal phosphorous trichalcogenide electrocatalysts (MPT 3 , where M = Fe, Ni; T = S, Se), achieving an exceptionally high OER activity in (Ni,Fe)P(S,Se) 3 , as demonstrated by its ultra-low Tafel slope (34 mV dec À 1 ) and a very low overpotential compared to many relevant OER catalysts. This is strongly supported by density functional theory calculations, which showed that this catalyst has a nearly optimal OER activity descriptor value of ΔG-(O*)À ΔG(OH*) = 1.5 eV. We also found that the activity descriptor is proportional to a newly proposed cation/anion complexity index that consists of pairwise contributions from cation-anion bonds in a catalyst compound, revealing the pivotal role of the cation-anion interactions in determining the catalyst performance and providing a simple way for predicting catalytic activities.