The synthesis of core/shell polymers with tunable mechanical properties made of poly(hexyl methacrylate) (PHeMA) and poly(methyl methacrylate) (PMMA) by a two‐stage semicontinuous heterophase polymerization, is presented here. This polymerization technique is characterized by employing low surfactant concentrations to produce large polymer‐to‐surfactant ratios. In this process, monomer is added in a continuous low rate to achieve monomer starved conditions, allowing to control particle size (usually smaller than 50 nm). To modulate the mechanical properties, the weight ratio of core/shell polymers are varied from 10/90 to 90/10 for direct and reverse compositions, respectively. Conversion was followed gravimetrically; nanoparticles were characterized with quasi‐elastic light scattering, IR spectroscopy, differential scanning calorimetry, transmission electron microscopy, and mechanical tests (tensile and hardness). Highly stable latex formed of nanoparticles, with high conversions are obtained. Tensile tests show that the mechanical properties can be tuned according to core/shell composition, mainly in the system formed by PMMA/PHeMA. These results are explained in terms of core‐and‐shell polymers location, composition and hardness. As expected, an increment in concentration of PMMA produces a more rigid material independently of its position. POLYM. ENG. SCI., 59:365–371, 2019. © 2018 Society of Plastics Engineers