Batch tests were carried out to study the effect of simultaneous addition of ethylenediaminetetraacetic acid and Ni2+ (EDTA-Ni) on anaerobic digestion (AD) performances of kitchen wastes (KWs). The results indicated that the cumulative biogas yield and methane content were enhanced to 563.82 mL/gVS and 63.7% by adding EDTA-Ni, respectively, which were almost 1.15 and 1.07-fold of that in the R2 with Ni2+ addition alone. At the same time, an obvious decrease of propionic acid was observed after EDTA-Ni addition. The speciation analysis of Ni showed that the percentages of water-soluble and exchangeable Ni were increased to 38.8% and 36.3% due to EDTA-Ni addition, respectively. Also, the high-throughput sequencing analysis revealed that the EDTA-Ni promoted the growth and metabolism of Methanosarcina and Methanobacterium, which might be the major reason for propionic acid degradation and methane production.