We report the synthesis of poly(styrene-block-lactic acid) (PS-b-PLA) copolymers with triazole rings as a junction between blocks. These materials were prepared via a ‘click’ strategy which involved the reaction between azide-terminated poly(styrene) (PS-N₃) and acetylene-terminated poly(D,L-lactic acid) (PLA-Ac), accomplished by copper-catalyzed azide-alkyne cycloaddition reaction. This synthetic approach has demonstrated to be effective to obtain specific copolymer structures with targeted self-assembly properties. We observed the self-assembly behavior of the PS-b-PLA thin films as induced by solvent vapor annealing (SVA), thermal annealing (TA), and hydrolysis of the as-spun substrates and monitored their morphological changes by means of different microscopic techniques. Self-assembly via SVA and TA proved to be strongly dependent on the pretreatment of the substrates. Microphase segregation of the untreated films yielded a pore size of 125 nm after a 45-min SVA. After selectively removing the PLA microdomains, the as-spun substrates exhibited the formation of pores on the surface, which can be a good alternative to form an ordered pattern of triazole functionalized porous PS at the mesoscale. Finally, as revealed by scanning electron microscopy–energy dispersive X-ray spectroscopy, the obtained triazole-functionalized PS-porous film exhibited some affinity to copper (Cu) in solution. These materials are suitable candidates to further study its metal-caption properties.