The wastewater industry is facing a paradigm shift, learning to view domestic wastewater not as a waste stream which needs to be disposed of but as a resource from which to generate energy. The extent of that resource is a strategically important question. The only previous published measurement of the internal chemical energy of wastewater measured 6.3 kJ/L. It has long been assumed that the energy content in wastewater relates directly to chemical oxygen demand (COD). However there is no standard relationship between COD and energy content. In this study a new methodology of preparing samples for measuring the internal chemical energy in wastewater is developed, and an analysis is made between this and the COD measurements taken. The mixed wastewater examined, using freeze-drying of samples to minimize loss of volatiles, had 16.8 kJ/L, while the domestic wastewater tested had 7.6 kJ/L nearly 20% higher than previously estimated. The size of the resource that wastewater presents is clearly both complex and variable but is likely to be significantly greater than previously thought. A systematic evaluation of the energy contained in wastewaters is warranted.