Biomass is increasingly being used for power generation; however, assessment of potential occupational health and safety (OH&S) concerns related to usage of biomass fuels in combustion-based generation remains limited. We reviewed the available literature on known and potential OH&S issues associated with biomass-based fuel usage for electricity generation at the utility scale. We considered three potential exposure scenarios—pre-combustion exposure to material associated with the fuel, exposure to combustion products, and post-combustion exposure to ash and residues. Testing of dust, fungal and bacterial levels at two power stations was also undertaken. Results indicated that dust concentrations within biomass plants can be extremely variable, with peak levels in some areas exceeding occupational exposure limits for wood dust and general inhalable dust. Fungal spore types, identified as common environmental species, were higher than in outdoor air. Our review suggests that pre-combustion risks, including bioaerosols and biogenic organics, should be considered further. Combustion and post-combustion risks appear similar to current fossil-based combustion. In light of limited available information, additional studies at power plants utilizing a variety of technologies and biomass fuels are recommended.