Heterojunction was built between TiO2 hollow spheres (THSs) and ZnIn2S4 (ZIS) flowers. Size discrepancy of THS and ZIS spheres contributes to a well-formed close packing. TiO2 hollowsphere in the composite possesses a “light collecting effect”. Optical and electrical tests confirmed the highly-efficient charge-carriers transfer. Photocatalysis mechanism was verified by OH monitoring and radical trapping experiments.