[TiO(salen)]n polymers are solubilised in aldehyde solution giving highly reactive entities. Unprecedented carbon‐based chemistry is demonstrated by the formation of new ligands about the titanium centre. Identified by X‐ray crystallography are a polymer deconstructed [Ti(salen)] oxo dimer, a [Ti(salen)] catecholato complex and an unusual [Ti(salen)] diolato complex. Formation of the new ligands appears to be related to the salicylidene ligand aromatic ring ortho substituent and the aldehyde used.