The convergent synthetic strategy for the poly(benzyl ether) dendrimers having the tetraethyleneoxide at core via the copper-catalyzed 1,3-dipolar cycloaddition reaction between alkyne and azide was described. Tetraethyleneglycol diazide, designed to serve as the core in dendrimer, was stitched with the alkyne-functionalized poly(benzyl ether) dendrons by the click chemistry leading to the formation of triblock dendritic polymers in high yields. The absorption and emission of the dendrimers were investigated. The structure of the dendrimers was characterized with H-1 NMR, C-13 NMR, and IR spectroscopies, mass spectra, and gel-permeation chromatography.