The influence of selenium dioxide (SeO2) on the microstructure and electrodeposition of manganese coatings obtained from a sulfate based neutral solution was investigated by material characterization methods and electrochemical techniques. The crystal structure and surface morphology of these coatings were studied by scanning electron microscopy (SEM) and powder X-ray diffraction spectroscopy (XRD), respectively. The SEM and XRD data showed that SeO2 could effectively accelerate phase transformation, and facilitate leveled and fine grain growth. The electrochemical results indicated that SeO2 could inhibit hydrogen evolution reaction and promote manganese deposition. The action of selenium dioxide in manganese deposition was found to be a reduction and adsorption mechanism. The process could be explained as following: First, Se (IV) was reduced to Se (0), and part of Se (0) future reduce to selenide, which then combined with the remainder Se (0) forming a complicate compound (multi-selenium ions). (C) 2011 Elsevier Ltd. All rights reserved.