In this study, we demonstrated that the choice of precursor has a strong effect on the reduction of nitrate (NO3−) using zero-valent copper (Cu0) synthesized by sodium borohydride (NaBH4). Different precursors: CuSO4, CuO, Cu2O, Cu powder, and Cu mesh were used to reduce NO3− at 677 mg-N/L under the reducing conditions of NaBH4. Compared with the prehydrolyzed samples, those prepared without prehydrolysis exhibited lower reduction rates, longer times and higher concentrations of nitrite (NO2−) intermediate. It was found that one-time addition of NaBH4 resulted in higher reduction rate and less NO2− intermediate than two-step addition. Results showed that Cu0 from CuSO4 possessed the smallest particle size (890.9 nm), highest surface area (26.0 m2/g), and highest reaction rate (0.166 min−1). Values of pseudo-first-order constant (kobs) were in the order: CuSO4 > CuO > Cu2O > Cu powder >Cu mesh. However, values of surface area-normalized reaction rate (kSA) were approximately equal. It was proposed that NO3− was reduced to NO2− on Cu0, and then converted to NH4+ and N2, respectively; H2 generated from both NaBH4 hydration and Cu (II) reduction contributed to NO3− reduction as well.