Interaction of p-tert-butylcalix[6]areneH6, L1H6, with [TiCl4] afforded the complex [Ti2Cl3(MeCN)2(OH2)(L1H)][Ti2Cl3(MeCN)3(L1H)]·4.5MeCN (1·4.5MeCN), in which two pseudo-octahedral titanium centres are bound to one calix[6]arene. A similar reaction but employing THF resulted in the THF ring-opened product [Ti4Cl2(μ3-O)2(NCMe)2(L)2(O(CH2)4Cl)2]·4MeCN (2·4MeCN), where LH4 = p-tert-butylcalix[4]areneH4. Interaction of L1H6 with [TiF4] (3 equiv.) led, after work-up, to the complex [(TiF)2(μ-F)L1H]2·6.5MeCN (3·6.5MeCN). Treatment of p-tert-butylcalix[8]areneH8, L2H8, with [TiCl4] led to the isolation of the complex [(TiCl)2(TiClNCMe)2(μ3-O)2(L2)]·1.5MeCN (4·1.5MeCN). From a similar reaction, a co-crystallized complex [Ti4O2Cl4(MeCN)2(L2)][Ti3Cl6(MeCN)5(OH2)(L2H2)]·H2O·11MeCN (5·H2O 11MeCN) was isolated. Extension of the L2H8 chemistry to [TiBr4] afforded, depending on the stoichiometry, the complexes [(TiBr)2(TiBrNCMe)2(μ3-O)2(L2)]·6MeCN (6·6MeCN) or [[Ti(NCMe)2Br]2[Ti(O)Br2(NCMe)](L2)]·7.5MeCN (7·7.5MeCN), whilst use of [TiF4] afforded complexes containing Ca2+ and Na+, thought to originate from drying agents, namely [Ti8CaF20(OH2)Na2(MeCN)4(L2)2]·14MeCN (8·14MeCN), [Na(MeCN)2][Ti8CaF20NaO16(L2)2]·7MeCN (9·7MeCN) or [Na]6[Ti8F20Na(MeCN)2(L2)][Ti8F20Na(MeCN)0.5(L2)]·15.5(C2H3N) (10·15.5MeCN). In the case of [TiI4], the ladder [(TiI)2(TiINCMe)2(μ3-O)2(L2)]·7.25CH2Cl2 (11·7.25CH2Cl2) was isolated. These complexes have been screened for their potential to act as catalysts in the ring opening polymerization (ROP) of ε-caprolactone (ε-CL), δ-valerolactone (δ-VL) and rac-lactide (r-LA), both in air and N2. For ε-CL and δ-VL, moderate activity at 130 °C over 24 h was observed for 1, 9 and 11; for r-LA, only 1 exhibited reasonable activity. In the case of the co-polymerization of ε-CL with δ-VL, the complexes 1 and 11 afforded reasonable conversions and low molecular weight polymers, whilst 4, 6, and 9 were less effective. None of the complexes proved to be active in the co-polymerization of ε-CL and r-LA under the conditions employed herein.