Novel, photocrosslinkable, star-shaped molecules have been synthesized by attaching a tricyanopyrroline (TCP)-based chromophore to 6-(4-{1,1-bis-[4-(5-carboxy-pentyloxy)-phenyl]-ethyl}-phenoxy)-hexanoic acid. The chromophore 2-(3-cyano-4-(4-diethylamino-phenyl)-5-oxo-1-{4-[4-(3-oxo-3-phenyl-propenyl)-phenoxy]-butyl}-1,5-dihydro-pyrrol-2-ylidene)-malononitrile is a second-order nonlinear optical active compound and bears a chalcone moiety that is sensitive to UV light (λ=320–350nm) for 2π+2π photocycloaddition. The resultant molecules exhibited good processability and showed 29–37pm/V of the maximum electro-optic coefficient at 1300nm.