Air pollutant distributions identified through monitoring form an important basis for devising adequate emergency responses against sudden air pollution accidents (SAPAs). However, studies on the optimisation of monitoring layouts for SAPAs, which can help us better understand air pollutant dispersion, are lacking. We developed an emergency monitoring layout optimisation method for SAPAs that combines an air pollutant dispersion model, a fuzzy comprehensive evaluation method (FCEM), and a post-optimality analysis technique (POAT) to identify the optimal monitoring layout scheme based on a field sulphur hexafluoride (SF6) leakage test. The impact of the number of monitoring sites on the results (coverage rate and accuracy) were investigated and analysed through a proposed comprehensive evaluation method. A monitoring result–monitoring number curve was plotted to determine the optimal number of monitoring sites. Two scenarios, i.e. with and without environmentally sensitive monitoring sites, were analysed. The results showed that the developed optimisation method can effectively consider the role of sensitive sites and obtain a feasible network for monitoring SAPAs. The coverage rates of the optimal monitoring layout schemes were 76.2% and 61.9% for the two case scenarios, respectively; the relative deviations of mean air pollutant concentrations at the sites were 14.6% and −12.2%, respectively. We investigated the effect of incorporating POAT into the method by comparing the optimal emergency monitoring layout schemes based on dispersion model–FCEM and model–FCEM–POAT. The results showed that the coverage rates of the optimised monitoring layout schemes improved when POAT was introduced. The proposed method can help determine an adequate, optimised emergency monitoring network for SAPAs.