Excessive Cr(VI) emissions have been and continue to be a major contributor to heavy-metal pollution; recently, the development of a low-cost, safe and efficient method for the removal of Cr has attracted significant attention. In the present study, a two-step method involving oxalic acid reduction and modified fly ash adsorption was developed. The experimental results showed that this methodology exhibited high Cr(VI) removal efficiency under the following conditions: 1.5 g L⁻¹ of oxalic acid, modification of fly ash (FA) by 20 wt% KOH, a contact time of 2 h and a mass of 0.3 g of modified fly ash (MFA) at room temperature (15–25 °C). The influencing factors of the adsorbent were discussed by characterized for their elemental composition, functional groups, surface area and surface morphology. According to the characteristic parameters and q_e, the isothermal adsorption process could be well-described by the Langmuir model. The adsorption process resembles more closely to the pseudo-second-order kinetic model. In conclusion, this two-step method of oxalic acid reduction-modified fly ash adsorption is promising for Cr(VI) removal.