•IRs and HS-GC-IMS were for the first time compared for olive oil classification.•Pros and cons using those techniques for the analysis of olive oil were gathered.•IRs reached classification success for ternary and binary olive oil classification.•HS-GC-IMS showed greater olive oil classification potential than IRs.•IRs can be preliminary olive oil screening tools, and HS-GC-IMS a confirmatory one. Virgin olive oil (OO) can be classified into three different categories: extra virgin, virgin and lampante. The official method for this classification, based on physicochemical analysis and sensory tasting, is considered useful and effective, although it is a costly and time-consuming process. The aim of this study was to assess the potential of some analytical techniques for classifying and predicting different OO categories to support official methods and to provide olive oil companies with a rapid tool to assess product quality. Thus, mid and near infrared spectroscopies (MIR and NIR) have been compared by using different instruments and with head-space gas chromatography coupled to an ion mobility spectrometer (HS-GC-IMS). High classification success rates in validation models were obtained using IR spectrometers (>70% and > 80% in average for ternary and binary classifications, respectively), although HS-GC-IMS showed greater classification potential (>85% and > 90%).