Biological techniques are widely used to treat gaseous streams derived from waste treatment plants. The generation of volatile organic compounds (VOCs) is one of the principal pollution sources in composting facilities from which nuisance odours are released. In addition, the generation of photochemical smog with other gases such as NOX can produce ozone at ground level due to their photochemical ozone creation potential (POCP). In this work, the performance of an industrial biofilter was evaluated from an environmental point of view. Specifically, this study evaluated the potential impact in terms of photochemical oxidation and odour emission derived from composting in a vessel under four different aeration conditions. Gas chromatography–time-of-flight mass spectrometry (GC-TOFMS) was used to perform the chemical characterisation of the gaseous streams, while dynamic olfactometry was used to carry out the sensorial analysis. A total of 95 compounds belonging to 12 different families of VOCs were selected. Principal component analysis revealed the influence of each VOC family on each impact category and explained 88% of the total variance. Multivariate regression was used to study the correlation between photochemical oxidation and odour impact, which has never been reported before. The correlations obtained (r ≥ 0.97) evidenced the direct relationship between these two impacts. Photochemical oxidation and odour emission were proven to be important environmental impacts derived from composting facilities, whose abatement might be carried out by biofiltration systems.