The selective adsorption performance of nanoscale humic acid based ion exchange composite resin for Ni2+/Cd2+ was investigated from multi-ionic co-existing system. On this basis, a novel resource recovery process for Ni/Cd wastewater, which included multi-column series, saturated adsorption and concentrated circulation, was developed. The micro-morphology, chemical structure, heat resistance, element composition change and pore size distribution of nanoscale humic acid based ion exchange composite resin were characterized by SEM, FTIR, TG-DTG, XPS and BET. The experimental results showed that the ion exchange composite resin had the advantage of fast adsorption rate [0.55—1.50 mg·(g·min)-1], high exchange capacity(139 or 148 mg·g-1 for Ni2+/Cd2+ on Ca2+ and Mg2+ coexisting system)and excellent selectivity behavior, high elution concentration and purity for Ni2+/Cd2+ (45.15 g·L-1 or 39.17 g·L-1, and QNi(Ⅱ)/Qtotal 0.989,QCd(Ⅱ)/Qtotal 0.994). After 200 adsorption-regeneration cycles, the physical and chemical structures of the adsorptive composite resin were still kept stable performance, and the section morphology and exchange capacity basically remain unchangeable, showing that it can be reused. The specific surface area, average pore diameter and pore volume were 1189.85 m2·g-1, 30.2 nm and 0.96 cm3·g-1, respectively with good thermal stability. The nitrogen content decreased from 16% to 12%, oxygen content increased from 26.49% to 29.96% and ionic exchange capacity rose from 5.38 mmol·g-1 to 6.06 mmol·g-1.