Modern wastewater utilities need to be able to measure and quantify the amount of methane from their treatment facilities in order to understand the potential energy that can be produced and the amount of methane being lost. This paper describes the application of a novel sampling bailer designed for the collection of wastewater samples that minimises methane losses. Samples collected during and following anaerobic treatment from a wastewater treatment plant using a novel sampling bailer were analysed using a previously optimised analytical method. Analysis of wastewater and anaerobic pond samples using current industry approaches resulted in dissolved methane concentrations ranging from 0.01 to 14.33 mg L−1. In comparison, the modified sampling protocol resulted in concentrations ranging from 0.08 to 18.73 mg L−1. The relative standard deviations (RSD%) of low level spikes (5.0 mg L−1 and 0.1 mg L−1 methane; n = 5) were found to be 2.3 and 10.3, respectively. Statistical analysis of the dissolved methane concentrations using the two different approaches demonstrated a significant difference in the recovered dissolved methane concentrations, indicating there is a greater methane recovery potential in wastewater treatment plants than previously realised, when collected using the novel sampling bailer and analysed following the optimised analytical protocol.