In order to improve the selectivity of allyl phenyl ether (ROPh), the main product, in the etherification of allyl bromide (RBr) and sodium phenolate (NaOPh) with tetra-n-butylammonium bromide (QBr) as a phase-transfer catalyst, the technique of tri-liquid-phase phase-transfer catalysis, instead of the liquid-liquid one, was employed. The reaction was performed in a batch reactor, and the factors affecting the conversion and selectivity were investigated. The possibility of reusing the phase-transfer catalyst was also evaluated. Experimental results indicate that the addition of a small amount of Na2CO3 will benefit the formation of a third liquid phase and enhances both the conversion of RBr and the overall yield of ROPh. Both the conversion and the overall yield are maximal when the mole fraction of QBr in the mixture of NaOPh and QBr is about 0.3. A high reaction temperature enhances the conversion and the overall yield. Under optimal conditions, complete conversion and near 100% yield can be obtained within 10 minutes. Although the reaction rate by the tri-liquid-phase catalysis is slightly lower than that observed with the same amount of catalyst by conventional liquid-liquid phase-transfer catalysis, the selectivity of ROPh is higher and the catalyst can be easily reused by the reuse of the third liquid phase without any loss of its catalytic activity in the former case. Because the reuse of catalyst was found to be feasible, the production of ROPh with a continuous-flow reactor becomes possible.