We model As2O3 glass from the liquid state using ab initio molecular dynamics simulations and probe its atomic structure using various analyzing techniques. The model is almost free from coordination and chemical defects and has an average coordination number of 238. The AsO3 pyramids are randomly connected via corner sharing to form the glass state. The glass network presents six membered hexagonal-like rings similar to those formed in the As4O6 molecules but isolated or complete As4O6 molecules do not exist. The glass state mainly consists of layer-like and incomplete As4O6-like structures. (C) 2016 Elsevier B.V. All rights reserved.