In this study, the reverse micelles from gemini surfactants pentamethylene-alpha,omega-bis(dodecyldimethylammonium bromide), dodecamethylene-alpha,omega-bis(dodecyldimethylammonium bromide), pentamethylene-alpha,omega-bis(cetyl-dimethylammonium bromide) and octamethylene-alpha,omega-bis(cetyldimethylammonium bromide) were used to extract bromelain from pineapple peel. The extraction parameters including pH, ionic strength and surfactant content were studied. It was found that the reverse micelle from dodecamethylene-alpha,omega-bis (dodecyldimethylammonium bromide) could extract more active bromelain in a much wider range of pH, surfactant content and ionic strength than the reverse micelles from the other gemini surfactants, and the optimum activity recovery, purification fold and protein extraction efficiency with dodecamethylene-alpha,omega-bis (dodecyldimethylammonium bromide) were 160 %, 2.7 and 59 %, respectively. Pineapple peel accounts for the largest waste proportion of pineapple. This study investigated the effect of gemini surfactant structure on extraction efficiency of bromelain from pineapple peel by reverse micelle extraction, and hence, should be helpful for understanding the potency of gemini surfactant in protein extraction.