We studied the possibility of monitoring with proton transfer reaction-mass spectrometry (PTR-MS) odours emitted in various situations related to composting plants of municipal solid waste (MSW), i.e., waste storage, waste management, and biofilters. Comparison of PTR-MS volatile profiles of the gaseous mixtures entering and exiting a biofilter suggests the possibility of fast and reliable monitoring biofilter efficiency. Moreover, we investigated the relationships between the olfactometric assessment of odour concentration and PTR-MS spectral line intensity finding a positive correlation between the former and several masses and their overall intensity. The application of multivariate calibration methods allows to determine odour concentrations based only on PTR-MS instrumental data. The possibility of avoiding the use of time consuming and expensive olfactometric methods and applications in monitoring waste treatments plants and, in particular, of biofilters is suggested.