AbstractGreen Lean Six Sigma has been recently clarified to improve the environmental sustainability performance of operations, but it seems glaringly scarce and in need of cutting‐edge studies to integrate the concepts of green, lean, and Six Sigma into one unified application. This paper is accordingly aimed at constituting the application of Green Lean Six Sigma as a cleaner production. In doing so, a Define, Measure, Analyze, Improve, and Control (DMAIC)‐based approach that is one of Six Sigma's well‐known methods was proposed to systematize a Green Lean tool—environmental value stream mapping. Thus, this paper as one of the preliminary studies aligns environmental value stream mapping with DMAIC through presenting the proposed methodological approach, which relies on the five DMAIC phases—Define, Measure, Analyze, Improve, and Control—and considers green wastes in each phase simultaneously. To support the narrow body of knowledge, this proposed approach was validated via the action research‐oriented case study implemented in the substrate manufacturing system that seeks to develop the environmental sustainability of its production processes and subsequently its general competitiveness. The findings indicated the effectiveness of a DMAIC‐based approach in systematizing environmental value stream mapping and improving its efficacy to achieve environmental sustainability. The case analysis revealed that the application can significantly lessen the consumption of chemicals and energy in the system by 28% and 21%, respectively.