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.

All‐aqueous, surfactant‐free, and pH‐driven nanoformulation methods to generate pH‐ and temperature‐responsive polymer nanoparticles (NPs) are described. Copolymers comprising a poly(methyl methacrylate) (PMMA) backbone with a few units of 2‐(dimethylamino)ethyl methacrylate (DMAEMA) are solubilized in acidic buffer (pH 2.0) to produce pH‐sensitive NPs. Copolymers of different molar mass (2.3–11.5 kg mol⁻¹) and DMAEMA composition (7.3–14.2 mol%) are evaluated using a “conventional” pH‐driven nanoformulation method (i.e., adding an aqueous polymer solution (acidic buffer) into an aqueous non‐solvent (basic buffer)) and a robotized method for pH adjustment of polymer dispersions. Dynamic light scattering, zeta‐potential (ζ), and sedimentation‐diffusion analyses suggest the formation of dual‐responsive NPs of tunable size (from 20 to 110 nm) being stable for at least 28 days in the pH and temperature intervals from 2.0 to 6.0 and 25 to 50 °C, respectively. Ultraviolet‐visible spectroscopic experiments show that these NPs can act as nanocarriers for the pH‐sensitive dipyridamole drug, expanding its bioavailability and potential controlled release as a function of pH and temperature. These approaches offer alternative strategies to prepare stimuli‐responsive NPs, avoiding the use of harmful solvents and complex purification steps, and improving the availability of biocompatible polymer nanoformulations for specific controlled release of pH‐sensitive cargos.