A solvent-free process is described for the synthesis of tailor-made molecules from a one-pot, two-step approach combining aza-Michael addition and photoinduced copper(I) catalysed azide–alkyne (photo-CuAAC) reactions. After the first reaction between an amine and an acrylate, cycloaddition between an azide and an alkyne is activated by light irradiation in the presence of a copper complex. The kinetics of the aza-Michael addition and photo-CuAAC reaction were investigated by liquid state ¹H NMR spectroscopy and real-time Fourier transform infrared spectroscopy. This new process represents a well-defined spatio-temporal pathway to the synthesis of bespoke intermediate molecules for various applications.