Abstract A photo‐assisted process is explored for improving the synthesis of oligo(triazole amide)s, which are prepared by solid phase synthesis using a repeated cycle of two reactions: amine‐carboxylic acid coupling and copper‐catalyzed azide‐alkyne cycloaddition (CuAAC). The improvement of the second reaction is investigated herein. A catalytic system involving Cu(II)Cl 2 , N , N , N’ , N ″, N ″‐pentamethyldiethylenetriamine (PMDETA) and a titanocene photoinitiator is explored for reducing the reaction time of CuAAC. This catalyst is first tested on a model reaction involving phenylacetylene and ethyl azidoacetate in DMSO. The kinetics of these model experiments are monitored by 1 H NMR in the presence of different concentrations of the photoinitiator. It is found that 30 mol% of photoinitiator leads to quantitative reactions in only 8 min. These conditions are then applied to the solid phase synthesis of oligo(triazole amide)s, performed on a glycine‐loaded Wang resin. The backbone of the oligomers is constructed using 6‐heptynoic acid and 1‐amino‐11‐azido‐3,6,9‐trioxaundecane as submonomers. Due to slow reagent diffusion, the CuAAC step required more time in the solid phase than in solution. Yet, one hour only is necessary to achieve quantitative CuAAC on the resin, which is twice as fast as previously‐reported conditions. Using these optimized conditions, oligo(triazole amide)s of different length are prepared.