Blast furnace slag samples with phase separation structure were prepared by re-melting and then water quenching process. By use of XRD,DTA and SEM technologies in combination with mechanical property experiment,the structure characteristics of samples were determined and their effects on cementitious reactivity were investigated. The results show that the samples with phase separation have better cementitious reactivity than sample with homogenous glass and sample with crystalline phases,which mainly contributes to its glass structure with coexistence of Ca-O rich phase and Si-O rich phase. Moreover,the amorphous samples possess hydrability which is affected by their formation process,since phase separation extends the range of possible Ca-rich crystalline phases. By using of XRD, DTA and SEM technologies in combination with mechanical property experiment, the structure characteristics of samples were determined and their effects on cementitious reactivity were investigated. The results show that the samples with phase separation have better cementitious reactivity than sample with homogenous glass and sample with crystalline phases, which mainly contributes to its glass structure with coexistence of Ca-O rich phase and Si-O rich phase. Moreover, the amorphous samples possess hydrability which is affected by their formation process, since phase separation extends the range of possible Ca-rich crystalline phases.