Polyphenols were extracted from the skin of jabuticaba fruits (Myrciaria cauliflora). Their total concentration and in vitro antioxidant activity were analysed by the DPPH and ABTS methods. The corresponding results (dry basis) were 1290 mg gallic acid equivalent (GAE)∙(100 g)−1, 98% of DPPH radical inhibition and 120 μm TEAC∙g−1 (ABTS method). All these values are at least as higher as average values reported in the literature for other fruits. A more specific analysis of the fractions of phenolic compounds was also performed by HPLC-MS. Ellagic acid, quercetin, rutin, delphinidin-3-glucoside and cyanidin-3-glucoside were the main compounds detected; the latter two were the most abundant. The crude extract was subjected to enzymatic acylation assays in order to synthesise new esters with new potential techno-functionalities. Palmitic acid was used as acyl donor and lipase B of Candida antactica (CALB) as biocatalyst. HPLC-MS evidenced the formation of palmitic monoesters in connection with the delphinidin-3-glucoside and cyanidin-3-glucoside fractions.