Star polymers with methacryloyl groups at the chain ends were synthesized by esterification of hydroxyl end-functional star polymers. First, the linear hetero-telechelic macroinitiator (MI) was prepared by ATRP using a functional initiator. The obtained MI was chain-extended and cross-linked with DVB and then esterified into methacryloyl chain-end functionality. The degree of esterification was controlled by changing the initial molar ratios of methacryloyl chloride to hydroxyl groups. The methacryloyl-containing star polymers were cross-linked either intermolecularly or intramolecularly under heating or UV irradiations, depending on the concentrations of star polymers during the cross-linking reactions.