The convergent synthetic strategy for the emissive poly(benzyl ether) dendrimers having the chromophore at core via the copper-catalyzed 1,3-dipolar cycloaddition reaction between alkyne and azide was described. 2,7-Diazido-9H-fluorene, 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 fluorescent poly(benzyl ether) dendrimers in high yields. The absorption and emission of the dendrimers were investigated. Their photophysical studies indicated that 2,7-diazido-9H-fluorene showed no fluorescence due to the quenching effect from the electron-rich alpha-nitrogen of the azido group but the dendrimers fluoresced due to the elimination of the quenching through the formation of the triazole ring.