The formation of rod-crystals was observed on CuInSe 2 thin films prepared by successive ionic layer adsorption and reaction (SILAR) method using sodium dodecylbenzene sulfonate (SDBS) as directing agent. Rod-crystals appeared on the surface of CuInSe 2 thin film when adding SDBS into cationic precursor solution. FESEM, EDS, XRD and HRTEM were used to characterize the rod-crystals. The length of rod-crystals has a proportional relationship with SDBS amounts in the given scope of 0.001–0.01 mol/L. The stoichiometry of rod was close to 1:1:2 of CuInSe 2, and rod growth of partially preferential orientation along [112] was observed. The growth of rod could be explained by steric hindrance effects of SDBS adsorbed on the inorganic deposit surface.