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A novel in-situ and green method with the combination of TiCl4 pre-treatment and solvothermal growth was proposed to prepare the Pt-free Cu2ZnSnS4(CZTS)counter electrodes(CEs)on FTO substrate.It was found that TiCl4 pre-treatment towards the substrates was crucial to high quality and high efficiency CZTS film,which was consists of nanosheets and nanoparticles structure.The highly crystallized nanosheets were assembled from kesterite-structure CZTS nanocrystals,with an average diameter of 10-30 nm.