Atom transfer radical polymerization (ATRP) was used to prepare poly(acetoxystyrene) (PAS) with a controlled molecular weight and narrow polyclispersity. Using 1-phenylethylbromide (PEBr)/CuBr/Cu(0)/2,2'-bipyridine as an initiating system, the heterogeneous ATRP of 4-acetoxystyrene was carried out to form PAS as a precursor polymer. The reaction follows the first-order kinetics with respect to the conversion of monomer. A linear molecular weight (polydispersities Mw/Mn = 1.07-1.27) indicates the "living" /controlled nature of polymerization. The obtained PAS was chemically modified to obtain succinylated poly(hydroxystyrene) (Succ-PHS). The formulation of Succ-PHS, crosslinker (benzoguanamine-formaldehyde), and triphenylsulfonium triflate (TPST) as a photo acid generator (PAG) was carried out by UV irradiation using an i-line tool. The performance of the resultant polymer as the negative resist pattern photoresist for photolithography was studied with instrumental techniques. (c) 2006 Wiley Periodicals, Inc.