Livestock is an important source of volatile organic compounds (VOCs) that can cause odor nuisance and pollution. The main sources of these VOCs in livestock are effluents and their management system. In this study, the applicability of headspace-solid phase microextraction coupled with gas chromatography-mass spectrometry (HS-SPME-GC-MS) for VOC characterization in effluent samples in both laboratory and field tests was evaluated. In the laboratory test, the VOC profile of different farm effluents (cattle dung, slurry and chicken droppings) was measured as well as the influence of the presence of litter material on their release. In the field test, a comparison was made between the VOC profile of two manure pits that had undergone treatment or not to assist in effluent management. The results presented here show that the HS-SPME-GC-MS technique allows one to quantify a wide spectrum of VOCs responsible for olfactory nuisances (177 and 73 VOCs in total for the laboratory and field tests, respectively) in a simple, fast, and economic way. This technique could be further developed to monitor olfactory nuisance markers and predict the evolution of different effluent materials.