Whisky, as a high value product, is often adulterated, with adverse economic effects for both producers and consumers as well as potential public health impacts. Here we report the use of DAPCI-MS to analyse and chemically profile both genuine and counterfeit whisky samples employing a novel 'direct from the bottle' methodology with zero sample pre-treatment, zero solvent requirement and almost no sample usage. 25 samples have been analysed from a collection of blended Scotch whisky (n = 15) and known counterfeit whisky products (n = 10). Principal component analysis has been applied to dimensionally reduce the data and discriminate between sample groups. Additional chemometric modelling, a partial least squares regression, has correctly classified samples with 92% success rate. DAPCI-MS shows promise for simple, fast and accurate counterfeit detection with potential for generic aroma profiling and process quality monitoring applications.