Agro-industrial wastes contain a number of valuable ingredients that can be re-used in the development and production of new added-value products. Among them, polyphenols are particularly interest compounds because of their known health-beneficial properties. The aim of this work was to define the procedure for fractionation of polyphenols and further to apply it for determination of polyphenols form pea pod. During fractionation, the polyphenols were isolated as fractions of free, conjugated – esterified and glycosylated, as well as bound compounds following liquid-liquid extraction, alkaline and acidic hydrolysis of the initial extract and alkaline hydrolysis of the residue after the initial extraction, respectively. The analysis of polyphenols was performed using HPLC-DAD method, specially developed to analyse 21 individual compounds from different polyphenolic subgroups. The addition of sodium chloride during liquid-liquid extraction, and further of ethyendiaminotetraacetic and ascorbic acid during alkaline hydrolysis, have markedly contributed to the stability and recovery of polyphenolic compounds. With the defined fractionation conditions, the model molecules of esterified and glycosylated polyphenols were successfiully hydrolysed, accompanied by relatively sufficient recovery of liberated compounds. Polyphenols in pea pod were mainly found as conjugates, as esters ofp-coumaric and sinapic acids, as well as quercetin glycosides, with contents of 207, 158 i 103 μg gdw.ˉ¹, respectively, while free and boundphenolics were minorly represented. Total phenolic content of concentrated initial pea pod extract exhibited 4.77 mgGAE gdwˉ¹ (Folin-Ciocalteu), accompanied by antioxidant capacity of 12.91 μmolTrolox gdw.ˉ¹ (DPPH). Pea pod can be established as relatively good source of polyphenols, the partial identification of which was largely enabled by the developed polyphenol fractionation procedure.