Sb2S3/perylene diimide derivatives composite micro-spheres composed of slight dendrites were synthesized by solvothermal reaction. Perylene diimide derivative with two carboxyl groups at amine position as morphology-controlling reagent is the key factor for determining the microscopic morphology of Sb2S3 in this system. Time-dependent experiments have been conducted to track the formation of Sb2S3 micro-spheres. Moreover, the composite material showed an excellent sensitivity of 29.8 mu A mM(-1) cm(2) with a low detection limit of 50 pM, it also showed better stability and selectivity in hydrazine detection. This approach not only regulate the morphology and composition of Sb2S3 submicron materials effectively, but also provide new ideas for the manufacture of metal sulfide- perylenediimide amino acid derivative materials, which will be suitable for sensing, catalysis, and photovoltaic applications.