A novel process involving the simultaneous electrochemical-oxidation (EO) and electrosynthesis of ferrate has been investigated for the treatment of the commonly detected and recalcitrant pesticide, atrazine. The present study considered the electrosynthesis of ferrate, in neutral pH, using low concentration iron (Fe2+) representative of raw water levels and its subsequent effect on atrazine degradation. Ferrate synthesis was unaffected by current density (10–80 mA cm−2), indicating mass transport limitations. Synthesis was affected by the initial iron concentration, whereby 0.051, 0.108 and 0.332 mg L−1 was generated with an Fe2+ concentration of 0.5, 1.0 and 3.0 mg L−1, respectively. When operating under simultaneous EO and ferrate oxidation, atrazine degradation exceeded that of a solely EO process. From an initial concentration of 2.00 mg L−1, atrazine was degraded to 1.34, 1.05 and 0.51 mg L−1 during 10, 40 and 80 mA cm−2, characterised by pseudo-first-order kinetics. Degradation with electrochemically-generated ferrate could be described by second-order kinetics, and yielded a degradation rate constant of 23.5 M−1 s−1. The effect of natural organic matter (NOM) on atrazine degradation was also investigated. Ferrate was observed to be mostly scavenged by resorcinol, a representative NOM compound, having a second-order reaction rate constant of 9.71 × 102 M−1 s−1.