The ability to control the outcome of polymerisations using an external stimulus remains a formidable challenge. Herein, we report a series of photoactive Schiff base ligands bearing azobenzene moieties, as well as seven Al(III) and Zn(II) complexes. Trans-cis isomerisation of the ligands and complexes occurred by exposure to UV light. Photoisomerisation was investigated using spectroscopic techniques and real-time reaction monitoring was conducted using FlowNMR. The activity of the complexes was tested in ring-opening polymerisation (ROP) of ε-caprolactone and rac-lactide under ambient and UV light conditions, with the isomers of the Al(III) complexes displaying marked differences in activity in the ROP of ε-caprolactone.