Reactions in three immiscible liquid phases (L-L-L) are attractive, and one of the phases can be the locale of reaction which will have a dramatic effect on product distribution in complex reactions. Thus, converting a bi-liquid system into a tri-liquid phase is of considerable scientific and commercial interest. 4-Benzyloxy-vanillin is used as a perfume and also as a starting material for synthesis of thalifoline and ephedradine as alkaloids and in synthesis of flavonoid compounds. Etherification of vanillin with benzyl chloride under biphasic phase transfer catalysis leads to formation of 4-benzyloxy-vanillin, but selectively suffers due to side reactions. Waste minimization is a major theme of green chemistry. In the traditional liquid-liquid phase transfer catalysis, the catalyst is not recovered but disposed off causing load on environment. However, the transformation of two-liquid phases into three-liquid phases L-L-L, PTC leads to 100% conversion of the limiting reactant benzyl chloride with 100% selectivity to 4-benzyloxy-vanillin, using TBAB as a catalyst. The rates of reactions are very high under L-L-L PTC, and reaction can be completed within 1 h as against 8 h required in L-L PTC. The catalyst-rich middle phase is recycled many times, thereby leading to profitability. The current work deals with effect of different kinetics and process parameters leading to enhancement in rates and selectivities and greener aspects of phase transfer catalysis. (c) 2005 Elsevier B.V. All rights reserved.