For many years, calorimetric measurements have been used for understanding, modelling, controlling, and optimising chemical reactions. Calorimetry could be as well utilised to investigate biological processes, which however, involve very small amount of heat and therefore require very sensitive instruments. For this purpose, a Mettler Toledo RCI (Reaction calorimeter) was modified, changing both hardware and software, increasing its resolution up to 5 10m W/l. Such sensitivity allows the monitoring of aerobic and anoxic processes. This paper points out the excellent agreement between calorimetric and respirometric data, obtained simultaneously under aerobic conditions using activated sludge from a lab-scale scale reactor. Heat production rate can be directly converted in oxygen uptake rate by means of a correlation factor, whose value is approximately the same for all aerobic respiratory metabolisms. Taking into account this factor, calorimetric data were introduced in a chemical oxygen demand based model and processed for the estimation of kinetic parameters of heterotrophic biomass. Aerobic heterotrophic, denitrifying, and autotrophic nitrifying activity were determined by specific calorimetric tests. The effect of potentially toxic or inhibitory substances on the activity of all microbial communities was as well pointed out in these measurements.