Advanced technologies call for composting indoors for minimized impact on the surrounding environment. However, enclosing compost piles inside halls may cause the accumulation of toxic pollutants, including carbon monoxide (CO). Thus, there is a need to assess the occupational risk to workers that can be exposed to CO concentrations > 300 ppm at the initial stage of the process. The objectives were to (1) develop a model of CO accumulation in the headspace of the bioreactor during organic waste composting and (2) assess the impact of headspace ventilation of enclosed compost. The maximum allowable CO level inside the bioreactor headspace for potential short-term occupational exposure up to 10 min was 100 ppm. The composting was modeled in the horizontal static reactor over 14 days in seven scenarios, differing in the ratio of headspace-to-waste volumes (H:W) (4:1, 3:1, 2:1, 1:1, 1:2, 1:3, 1:4). Headspace CO concentration exceeded 100 ppm in each variant with the maximum value of 36.1% without ventilation and 3.2% with the daily release of accumulated CO. The airflow necessary to maintain CO < 100 ppmv should be at least 7.15 m3·(h·Mg w.m.)−1. The H:W > 4:1 and the height of compost pile < 1 m were less susceptible to CO accumulation.