An accelerated solvent extraction method was used to recover polyphenol-rich crude extract from rambutan (Nephelium lappaceum L.) peel, a waste product from the canning industry. The influence of extraction parameters including temperature, extraction time and ethanol concentration on extraction yield, total phenolic content, total anthocyanin content, and ABTS antioxidant activity was investigated. A Box-Behnken design and response surface methodology were used to optimize the extraction process. Optimal conditions were obtained at temperature, extraction time, and ethanol concentration of 60 °C, 34 min, and 54 vol%, respectively. These optimum conditions gave 333.01 ± 5.84 mg gallic acid/g, 318.28 ± 5.56 mg cyanidin-3-O-glucoside/g, and 3.05 ± 0.04 mmol Trolox/mg for total phenolic content, total anthocyanins content, and ABTS activity, respectively with extraction yield of 28.68 ± 1.48 wt%. Important active compounds found in the extract were geraniin, ellagic acid, shikimic acid and corilagin. Crude extract concentrations of 50–500 mg/kg retarded linoleic acid oxidation but efficacy was lower than synthetic antioxidants at 200 mg/kg. The current findings indicated that accelerated aqueous ethanol extraction was an effective method for the recovery of a crude extract rich in polyphenols from rambutan peel with the potential to be used as a natural antioxidant.