The acetyl esterified calixarene (CA) derivatives were prepared from calix[4]resorcinarene (CRA), and p-tert-butylcalixarene (BCA[n], n = 4, 6, 8), respectively. Using these CA derivatives as curing agents, the thermal curing reactions of two multifunctional epoxy resins (jER 828, 186 g/equiv., and ESCN, 193.7 g/equiv.) were investigated. The temperatures of glass transition (T-g) and decomposition (T-d(10%)) were measured by DSC and TGA, respectively. Based on the yields, T(g)s, and T(d)s of the thermal cured jER 828 epoxy resin with CRA-E100, the curing conditions were optimized to be tetrabutylphosphonium bromide (TBPB) as catalyst in NMP at 160 degrees C for 15 h. Under this curing condition, the cured materials of jER 828 or ESCN using various CA derivatives as curing agents were prepared. Except for BCA4 derivatives, the yields of thermal curing reaction were higher than 90%. T(g)s and T(d)(10%)s of the resultant cured materials were in the range of 113-248 degrees C and 363-404 degrees C, respectively. These results mean that the cured epoxy resins with excellent T(g)s were successfully formed by using CA derivatives as curing agents. It was also found that the T(g)s of cured epoxy resins were strongly affected by the degree of esterification of CA derivatives. (C) 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 1931-1942, 2010