Ni-EDTA is a common heavy metal complex found in electroplating wastewater. As heavy metal complexes are stable and highly toxic, it is essential to develop efficient strategies to remove. In this work, TiCl3 coagulation and ceramic microfiltration membrane were combined in the removal of Ni-EDTA. Based on the results, this combinative process exhibited a high Ni-EDTA removal efficiency. When compared to employing the TiCl3 coagulation process only, the combinative process improved Ni2+ and TOC removal efficiencies from 91 % to 97 % and from 60 % to 93 %, respectively. Furthermore, it was found that the in-situ formed titanium hydrolysates possessed good adsorption for EDTA and Ni-EDTA, with maximum capacities reaching 713 mg/g and 213 mg/g, respectively, which also enabled the cake layer a considerable secondary removal for TOC. Mechanistic investigations confirmed that the reducibility of Ti3+ contributed to both Ni-EDTA and EDTA removal. In the presence of Ti3+, Ni-EDTA was decomplexed and the released Ni2+ was reduced to Ni0 synchronously. Meanwhile, some dissociated EDTA would combine with oxidized Ti4+ to form Ti-EDTA and ultimately promote the formation of TiO2 crystals. The formation of the insoluble chelate Ti-EDTA and the adsorption by surface hydroxyl of TiO2 were the key reasons for the efficient removal for released EDTA. This work provides a new approach for the decomplexation and harmless separation of heavy metal complexes.