Metalation of (RSiMe 2) 3CH ( 1a R = H, 1b R = Me, 1c R = Ph) with lithium diisopropylamide (LDA) or methyllithium in THF gave organolithium reagents (RSiMe 2) 3CLi, which reacted with the formylated calixarene ( 2), to give the corresponding 5,17-bis[2,2-bis(organosilyl)-1-ethenyl]-25,26,27,28-tetrapropoxycalix[4]arenes ( 3a, 3b and 3c) via the Peterson olefination. The compounds (RSiMe 2) 3CLi were treated with 25,26,27,28-tetrakis(4-bromobutoxy)calix[4]arene ( 4) to give 25,26,27,28-tetrakis[4-(tris(dimethylsilyl)methyl)butoxy] calix[4]arene ( 5a) and 25,26,27,28-tetrakis[4-(tris(trimethylsilyl)methyl)butoxy] calix[4]arene ( 5b) via nucleophilic substitution reactions. However the compound 25,26,27,28-tetrakis[4-(tris(dimethylphenylsilyl)methyl)butoxy] calix[4]arene ( 5c) was not obtained, presumably because (PhSiMe 2) 3C- is highly sterically hindered and the reactivity of its derivatives is low. The compound 5a has potential as a core for dendrimers.