Volatile Organic Compounds (VOCs) are produced by plants to address a variety of physiological and ecological tasks (among others, stress resistance, and pollinator attraction). Genetics is a key factor in determining plants’ VOCs content and emission, nevertheless, environment strongly influences VOCs profiles in plants. Orchids are a widespread group of plants that colonize diverse environments and rely on complex and refined pollination mechanisms to reproduce. Orchids VOCs are rarely studied and discussed in relation to growing conditions. In the present study, we compare the volatile profiles of inflorescences of Himantoglossum robertianum (Loisel.) P. Delforge sampled in six ecologically diverse populations on Sardinia Island (Italy). The essential oils obtained by steam distillation were characterized by GC-FID and GC-MS analysis. A total of 79 compounds were detected, belonging to the chemical classes of saturated hydrocarbons, esters, alcohols, ketones, unsaturated hydrocarbons, sesquiterpenes, oxygenated terpenes, terpenes, acids, and aldehydes. Multivariate statistics separated H. robertianum populations based on their chemical profiles. Differences were positively linked to the distance separating populations and reflected climatological features of the sampling sites. Interestingly, our results differed from those available in the literature, pointing out the high variability of VOCs profiles in this food-deceptive orchid.