A novel high efficient p-n heterostructure photocatalyst is well designed and firstly realized on coupling electrospun TiO2 anatase/rutile mixed-crystal nanorods (T-A/R-NRs) and p-type ternary Cu3SnS4 (CTS), which is a hot photosensitive material in photovoltaics but rarely attracted in photocatalysis. Such configured CTS@T-A/R-NRs shows 2.02 eV band-gap and are demonstrated to be more efficient in photocatalytic degradation. The optimized CTS@T-A/R-NRs with 24 h hydrothermal reaction possesses a superior degradation rate of 1.3980 h(-1), which is 2.5 and 4.3 times than T-A/R-NRs (0.5490 h(-1)) and CTS (0.3240 h(-1)). It is mainly attributed to the better morphology for high light-harvesting, the established built-in electric field at p-n interfaces and special anatase/rutile mixed-crystal structure of TiO2 for efficient separation of photogenerated charges. The study indicates a promising strategy in designing potential nanostructures to simultaneously achieve high efficient photocatalytic degradation and photovoltaic conversion. (C) 2018 Elsevier B.V. All rights reserved.