A stable water-in-oil (W/O) emulsion was prepared using polymeric additive as emulsifier instead of surfactant Span 80 (sorbitan monooleate) and kerosene as the organic membrane phase. The rubber emulsifiers were prepared using polybutadiene-styrene rubber (PBSR) or polybutadiene rubber (PBR) as the polymeric additive in this work. It was found that the rubber emulsifier acted like a surfactant in the emulsification process. The factors of influence of the W/O emulsion stability were investigated. The emulsion stability and mass transfer efficiency were assessed by measuring the concentration of nicotine in the internal strip and the external feed phase, respectively. The rheological behavior of W/O emulsion prepared with the rubber emulsifiers was also compared with that of W/O emulsion prepared with Span 80. It showed that the W/O emulsions prepared with the rubber emulsifiers were non-Newtonian when it dispersed in a continuous aqueous solution at low stirring speed. Applying the W/O emulsion for extraction of nicotine from real tobacco samples was carried out through dispersing it in the tobacco nicotine extractant aqueous solution. The results showed that nicotine was almost transferred from the feed to strip phase in 2 min and the efficiency of nicotine mass transfer was exceeded 99%. (C) 2015 Elsevier B.V. All rights reserved.