In the hemp industry, retting is an upstream bioprocessing applied to the plants to facilitate the decortication of fibres from the central woody part of the stem. This treatment is currently carried out in an empirical way on the ground which leads to variability in the hemp stems quality, and thus to the hemp fibres quality. Therefore, controlling retting treatment is a crucial step for high-performance hemp fibre. In this study, a new approach is used to assess the retting degree by following the evolution of VOCs emitted by plants during different retting durations. Either harvest time or retting induces a change in VOCs released by plants. During plant maturity, volatile compounds emitted decreased with a factor of about 2, in relation to VOCs released at the end of flowering. Regardless of the harvest period, the majority of VOCs and odor concentrations, monitored by olfactometric analysis, decrease gradually until some of them disappear at the end of retting. Likewise, the green plant odor disappears during retting with an increase of dry plants odor and an appearance of fermented odor at the end of retting. Following the evolution of VOCs emitted by plants during retting could be a tool for farmers to improve the retting management.