An analytical method for the determination of toxicological relevant species of arsenic in urine was developed and validated using hydride generation microwave-induced emission spectrometry (HG-MP-AES). This strategy can be used as an alternative to HG-HPLC-ICP-MS considered as a reference technique for arsenic speciation. This procedure is notably less expensive than other techniques and sample preparation and requires only a few steps. • Hydride generation with MP-AES detection has proven to be an effective technique for mea- suring arsenic metabolites in urine, which is relevant for occupational monitoring and health risk assessment purposes. • This method offers simplicity and cost-effectiveness, serving as an alternative to classical analytical procedures typically used for arsenic analysis in urine. • The methodology has been successfully applied for the purpose of workers’ health surveil- lance.