<p>Food authentication has become a critical issue for consumers, producers, and regulatory authorities, particularly for high-value products such as olive oil, which is highly susceptible to adulteration. In recent years, vibrational spectroscopy techniques, including mid-infrared (MIR), near-infrared (NIR), and Raman spectroscopy, have attracted significant attention as rapid and non-destructive analytical tools for assessing the authenticity of olive oil. When combined with multivariate chemometric approaches, these techniques enable the extraction of meaningful spectral fingerprints and the development of predictive models for adulteration detection. This review provides a comprehensive evaluation of studies conducted over the past decade, with a focus on the application of vibrational spectroscopy coupled with chemometrics for the authentication of olive oil. The reviewed studies demonstrate that combining vibrational spectroscopy with chemometric methods offers advantages, including minimal sample preparation, rapid analysis, environmental sustainability, and potential suitability for routine quality control and official food inspection. The current limitations and future research directions are also highlighted to facilitate the extensive implementation of these techniques in olive oil authentication frameworks.</p>