The temperature tuning effect in coordination reaction with the oligomer ligand, sodium [N-(4-O-phenyldithiocarboxylate) maleimide] n (n=10–15), has been studied. It is found that more Ti–S coordination bonds have been formed with reaction temperature increasing, which results in the variations in crystallinity, morphology and solid fluorescence of the prepared complex materials. The nature of temperature tuning is to improve the activity of oligomer ligands and increase the contacting probability between Ti(IV) and –CS 2 groups. Based on the experiment results, a Ti–S tetrahedral coordination model is also proposed for this case.