Display omitted •Innovative coupling of laser desorption to GC – ion mobility spectrometry (GC/IMS).•Rapid, sensitive and mobile detection.•Comprehensive characterisation of liquid samples based on volatiles.•Additional analysis of semi- and non-volatiles.•GC/IMS analysis of olive oil. The investigation of volatile compounds in the headspace of liquid samples can often be used for detailed and non-destructive characterisation of the sample. This has great potential for process control or the characterisation of food samples, such as olive oil. We investigated, for the first time, the plume of substances released from olive oil droplets by laser desorption in a feasibility study and applied ion mobility spectrometry coupled to rapid GC pre-separation to enhance selectivity. Our investigation demonstrated that significantly more substances can be detected and quantified via laser desorption than in the usual headspace, enabling a rapid (5–10 min), sensitive (low ng/g range) and comprehensive analysis of the sample, with the potential for quality control and fraud identification. Therefore, laser desorption provides a useful sampling tool for characterising liquids in many applications, requiring only a few µL of sample.