Reaction of 5,11,17,23-tetra-tert-butyl-dihydroxy-26,28-bis(2-pentoxy)calix[4]arene (L(OH)2(Opentyl)2) with [TiCl4] afforded the dichlorotitanoacalix[4]arene complex [TiCl2L(O)2(Opentyl)2] (1) in good yield. Hydrolysis of 1 led to the isolation of the complex {[TiL(O)3(Opentyl)]2(μ-OH)(μ-Cl)} (2). Reaction of 5,11,17,23,29,35,41,47-p-tert-butyl-49,50,51,52,53,54,55,56-octapropoxycalix[8]arene (L'(Opropyl)8) with [TiCl4] in refluxing toluene afforded, following work-up, a 35 : 65 mixture (3) of the complex [Ti(NCMe)Cl]2[TiCl(μ-O)]2L' and the silicone grease derived complex [Ti(NCMe)Cl]2[Ti(μ-O)]2[OSi(CH3)2OSi(CH3)2O]L' in which the grease replaces two chloride ligands. The molecular structures of 1·2MeCN, 2·7¼MeCN, and 3·10MeCN have been determined. The complexes were studied using in vitro cell assays and were found to have CC50 values in the range 111-186 μM, i.e. they have low toxicity.