In this study, tri-n-butylamine was immobilized on the merchant chloromethylated polystyrene (CMPS) to prepare the triphase catalyst for catalyst for catalyzing the etherification reaction to synthesize n-butyl phenyl ether from n-butyl bromide and sodium phenolate. The factors influencing the immobilization reaction include the physical properties of the polymeric support (extent of chloromethylation, degree of crosslinking, particle size), temperatures, kind of solvent, and amount of tri-n-butylamine were investigated. Experimental results indicate that, in immobilization reaction procedure, the nucleophilic reaction between tri-n-butylamine and chloromethy1 group in support occurs almost on the exterior surface of the catalyst particles and it is the rate-limlting step of the overall immobilization procedure, so the mass transfer resistance may be negligible. In addition, using an aprotic solvent (N,N-dimethylformamide, DMF), a high extent of chloromethylation, high reaction temperature, and high molar ratio of tri-n-butylamine to chloromethy1 group in supports are beneficial to the immobilization reaction. The triphase catalyst prepared to synthesize n-butyl phenyl ether can obtain higher reaction rate and convertion of n-butyl bromide. Nevertheless, both rate and the equilibrium extent of the immobilization reaction are slightly by the degree of crosslinking and the size of the catalyst.