In this paper, nickel ion and cobalt ion were separated from multimetal ionic solution system using P507/P204 as extraction agent by different two separation process. The extraction process parameters were calculated according to the theory of multistage countercurrent extraction, and the extraction experiment of two different processes were carried out based on the calculated process parameters, the results show that the raw liquid was extracted with P507 at first, the nickel ion was separated from multiple metal ion raw solution and the recovery rate value was up to 99.69%, the recovery rate of cobalt was 98.19%, when the raw liquid was extracted with P204 at first, nickel and cobalt were separated from the raw liquid at simultaneously and then P507 was used to separate nickel and cobalt, by this method, the recovery rate of nickel was 98.39%, the recovery rate of cobalt was 96.59%. Therefore, high recovery rate of nickel and cobalt could be obtained when P507 as extraction agent was used to separate nickel ion from multimetal ion solution initially. 