Human skin is a region of high metabolic activity where a rich variety of biomarkers are secreted from the stratum corneum. The skin is a constant source of volatile organic compounds (VOCs) derived from skin glands and resident microbiota. Skin VOCs contain the footprints of cellular activities and thus offer unique insights into the intricate processes of cutaneous physiology. This review examines the growing body of research on skin VOC markers as they relate to skin physiology, whereby variations in skin-intrinsic and microbial metabolic processes give rise to unique volatile profiles. Emerging evidence for volatile biomarkers linked to skin perturbations and skin cancer are examined. Microbial-derived VOCs are also investigated as prospective diagnostic markers, and their potential to shape the composition of the local skin microbiota, and consequently cutaneous health, is considered. Finally, a brief outlook on emerging analytical challenges and opportunities for skin VOC-based research and diagnostics is presented.