A novel hyperbranched polymer endcapped with 4-methylcoumarin group (MCTH40) was prepared via thiol-ene addition reaction of thiol-modified hyperbranched polyester (fully thioglycolic acetate of Boltorn (TM) H40, TAH40) with a vinyl monomer (7-(4-vinyl-benzyloxyl)-4-methylcoumarin, VBMC), and characterized with H-1 NMR and FT-IR spectroscopies. Its reversible photo-crosslinking/photo-cleavage behavior was evaluated based on the UV-vis spectroscopic analysis, and compared with the linear polymer, poly(7-(4-vinyl-benzyloxyl)-4-methylcoumarin (PVBMC)). The absorbance at 319 nm in the UV-vis spectrum gradually decreased under UVA irradiation (lambda(max) = 365 nm), and then rapidly recovered under UVC irradiation (lambda(max) = 254 nm). The fluorescence intensity of MCFH40 (lambda(max) = 469 nm) recovered to 85.2% of original level after photo-cleavage under UVC irradiation, higher than 83.5% of PVBMC (lambda(max) = 472 nm). The UV-vis analysis results indicated that MCTH40 performs more rapid photo-response than linear PVBMC under the same conditions. Furthermore, the average doses of UVA irradiation for the maximum degree of photo-crosslinking were 22.08 J cm(-2) for MCFH40 and 28.29J cm(-2) for PVBMC. The average UVC doses of complete photo-cleavage were 9.44 J cm(-2) for MCTH40 and 9.58 J cm(-2) for PVBMC. The GPC analysis indicated that the average molecular weight and its PDI of MCTH40 showed a slight increase after three reversible cycles. (C) 2008 Elsevier Ltd. All rights reserved.