New waste management programs are currently aimed at developing alternative treatment technologies such as mechanical–biological treatment (MBT) and composting plants. However, there is still a high uncertainty concerning the chemical and microbiological risks for human health, not only for workers of these facilities, but also for the population living in the neighborhood. A new MBT plant is planned to be constructed adjacently to a municipal solid waste incinerator (MSWI) in Tarragona (Catalonia, Spain). In order to evaluate its potential impact and to differentiate the impacts of MSWI from those of the MBT when the latter is operative, a pre-operational survey was initiated by determining the concentrations of 20 volatile organic compounds (VOCs) and bioaerosols (total bacteria, Gram-negative bacteria, fungi and Aspergillus fumigatus) in airborne samples around the MSWI. The results indicated that the current concentrations of bioaerosols (ranges: 382–3882, 18–790, 44–926, and