The selection of product portfolios, processing routes and the combination of technologies to obtain a sustainable biorefinery design according to economic and environmental criteria represents a challenge to process engineering. The aim of this research is to generate a robust methodology that assists process engineers to conceptually optimise the environmental and economic performances of biorefinery systems. A novel economic value and environmental impact (EVEI) analysis methodology is presented in this paper. The EVEI analysis is a tool that emerges from the combination of the value analysis method for the evaluation of economic potential with environmental footprinting for impact analysis. The methodology has been effectively demonstrated by providing insights into the performance of a bioethanol plant as a case study. The systematisation of the methodology allowed its implementation and integration into a computer-aided process engineering (CAPE) tool in the spreadsheet environment.