By combining nitric acid etching and Ni-assisted etching, the antireflective complex structure on multicrystalline silicon surface is prepared. Effects of the sputtering time of Ni on the performances including surface reflectance, morphology and photoluminescence property are studied. The surface reflectance of the multicrystalline silicon wafers is analyzed by spectrophotometer. The morphologies are observed by scanning electron microscopy and the photoluminescence properties are analyzed by photoluminescence measurement system. It is found that U-shaped etching pits with many needle-like structures inside are formed after the combined nitric acid etching and Ni-assisted etching. The results show that this kind of complex microstructures can significantly reduce the surface reflectance. The minimum surface reflectance in the range from 300 nm to 900 nm is only 10.1% when the sputtering time of Ni is 500 s.