The chemical characterization of local Italian potato cultivars is reported to promote their preservation and use as high quality raw material in food industries. Twenty potato (Solanum tuberosum L.) cultivars from Piedmont and Liguria Italian regions were investigated using NMR (Nuclear Magnetic Resonance) and RP-HPLC-PDA-ESI-MSn (Reversed Phase High-Performance Liquid Chromatography with Photodiode Array Detector and Electrospray Ionization Mass Detector) methodologies. Water soluble and lipophilic metabolites were identified and quantified. With respect to literature data, a more complete 1H (protonic) spectral assignment of the aqueous potato extracts was reported, whereas the 1H NMR assignment of potato organic extracts was reported here for the first time. Phenolics resulted to be in high concentrations in the purple–blue colored Rouge des Flandres, Bergerac, Fleur Bleu, and Blue Star cultivars. Servane, Piatlina, and Malou showed the highest amount of galacturonic acid, a marker of pectin presence, whereas Jelly cultivar was characterized by high levels of monosaccharides. Roseval and Rubra Spes contained high levels of citric acid involved in the inhibition of the enzymatic browning in fresh-cut potato. High levels of the amino acids involved in the formation of pleasant-smell volatile compounds during potato cooking were detected in Rouge des Flandres, Blue Star, Bergerac, Roseval, and Ratte cultivars. These results suggest that each local cultivar is characterized by a proper chemical profile related to specific proprieties that can be useful to obtain high quality industrial products.