The chemical industry is increasingly looking toward sustainable technology to reduce the environmental impact and minimize the footprint of a chemical process. This work, which presents emerging technologies in academia and industry, discusses the development of advanced processes for the production Of epoxidized plant oil-based plasticizers. The effects of the substrate structure, oxygen-donor properties, catalysts and biocatalysts on the specificity of the epoxidation reaction are intensively discussed. The progress in enzymatic epoxidation and the application of neoteric media, such as ionic liquids, are also highlighted. Particular attention is given to understanding how the emerging processes, including the new catalysts and novel reaction systems, work to dictate the reaction efficiency and selectivity. Hence, this review will be of value for developing further improved processes. (c) 2012 Elsevier Ltd. All rights reserved.