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Assessing the financial impact of polymers of intrinsic microporosity, otherwise known as PIMs, at the lab scale has been impeded by the absence of a holistic approach that would envelop all related financial parameters, and most importantly any indirect costs, such as laboratory accidents that have been consistently neglected and undervalued in past assessments. To quantify the cost of PIMs in relation to the risks befalling a laboratory, an innovative cost evaluation approach was designed. This approach consists of three stages. Firstly, a two-fold “window of opportunity” (WO) theory is suggested, dividing the total cost profile into two segments, followed up by a qualitative risk analysis to establish the potential cost components. The last stage builds on a total cost of ownership model, incorporating the two types of WO. The total cost of ownership (TCO) approach was selected to ascertain the costs and construct the cost profile of PIMs, according to laboratory experimental data. This model was applied to the synthesis and physicochemical characterization processes. The quantitative analysis revealed that the most influential parameters for synthesis are accidents and energy costs. This is in contrast with the physicochemical characterization process, where the most important determinant is the energy cost.