Volatile organic compound (VOC) off-gassing behavior of thermally treated biomass intended for bioenergy production has recently been shown to be vastly different from that of untreated biomass. Simple measures to reduce emissions, such as controlled ventilation and prolonged storage time, have been suggested but not yet studied in detail. In the present study, we monitored how VOC off-gassing was reduced over time (24–144 h) in enclosed storage with and without ventilation. Steam-exploded bark was collected directly from a pilot-scale steam explosion plant as well as before and after subsequent pelletizing. Active Tenax-TA absorbent sampling of VOCs was performed from the headspaces of a bench-scale sample storage setup. The impact of storage time and ventilation on VOC levels was evaluated through multivariate statistical analysis. The results showed that relative VOC concentrations in the headspace were reduced by increased storage time, with heavier VOCs reduced at a higher rate. VOC composition was neither reduced nor shifted by controlled intermittent ventilation during storage; instead, VOC levels equilibrated at the same levels as those stored without ventilation, and this was independent of the process step, storage time, or number of ventilations.