HPLC-UV was applied to the analysis and characterization of olive oils and other vegetable oils. A chromatographic separation on a Zorbax Eclipse XDB-C8 reversed-phase column was proposed under gradient elution, employing 0.1% formic acid aqueous solution and methanol as mobile phase, for the determination of 14 polyphenols and phenolic acids, allowing to obtain compositional profiles in less than 20 min. Acceptable sensitivity (LOD values down to 80 µg/L in the best of cases), linearity (r2 higher than 0.986), good run-to-run and day-to-day precisions (RSD values lower than 11.5%), and method trueness (relative errors lower than 6.8%) were obtained. The proposed HPLC-UV method was then applied to the analysis of 72 oil samples (47 olive oils and 27 vegetable oils including sunflower, soy, corn, and mixtures of them). Analytes were recovered by liquid-liquid extraction method employing ethanol:water 70:30 (v/v) solution and hexane as extracting and defatting solvents, respectively. HPLC-UV polyphenolic profiles using peak areas were then analysed by principal component analysis (PCA) to extract information of the most significant data contributing to the characterization and classification of olive oils against other vegetable oils, as well as among Arbequina and Picual olive oil varieties. PCA results showed a noticeable separation among olive oils and the other classes. Besides, a reasonable discrimination of olive oils as a function of fruit varieties was also encountered.