Biochar, as a cost-efficient adsorbent, is of major interest in the removal of heavy metals from wastewater. Herein, batch experiments were conducted to investigate the performance of biochar derived from rice straw for the removal of Ni(II) as a function of various environmental conditions. The results showed that Ni(II) sorption was strongly dependent on pH but independent of ionic strength and the effects of electrolyte ions could be negligible over the whole pH range. Ionic exchange and inner-sphere surface complexation dominated the sorption of Ni(II). Humic/fulvic acids clearly enhanced the Ni(II) sorption at pH <7.2 but inhibited the sorption at pH >7.2. The sorption reached equilibrium within 10 hours, and the kinetics followed a pseudo-second-order rate model. Any of the Langmuir, Freundlich, or Dubinin-Radushkevich isotherm models could describe the sorption well, but the Langmuir model described it best. The maximum sorption capacity calculated from the Langmuir model was 0.257 m·mol/g. The thermodynamic parameters suggested that Ni(II) sorption was a spontaneous and endothermic process and was enhanced at high temperature. The results of this work indicate that biochar derived from rice straw may be a valuable bio-sorbent for Ni(II) in aqueous solutions, but it still requires further modification.