This paper describes a new heat transfer parameterisation between wastewater and insewer air based on understanding the physical phenomena observed in free surface wastewater and in-sewer air. Long-term wastewater and in-sewer air temperature data were collected and studied to indicate the importance of considering the heat exchange with in-sewer air and the relevant seasonal changes. The new parameterisation was based on the physical flow condition variations. Accurate modelling of wastewater temperature in linked combined sewers is needed to assess the feasibility of in-sewer heat recovery. Historically, the heat transfer coefficient between wastewater and in-sewer air has been estimated using simple empirical relationships. The newly developed parameterisation was implemented and validated using independent long-term flow and temperature datasets. Predictive accuracy of wastewater temperatures was investigated using a Taylor diagram, where absolute errors and correlations between modelled and observed values were plotted for different site sizes and seasons. The newly developed coefficient improved wastewater temperature modelling accuracy, compared with the older empirical approaches, which resulted in predicting more potential for heat recovery from large sewer networks. For individual locations, the RMSE between observed and predicted temperatures ranged between 0.15 and 0.5 °C with an overall average of 0.27 °C. Previous studies showed higher RMSE ranges, e.g., between 0.12 and 7.8 °C, with overall averages of 0.35, 0.42 and 2 °C. The new coefficient has also provided stable values at various seasons and minimised the number of required model inputs.