The influence of the amounts of acrylic acid, chain transfer agent and anionic stabilizer on polymer microstructural properties and final adhesive performance of BA/VAc emulsion-based PSAs on stainless-steel and high-density polyethylene substrates was investigated using a Box-Behnken experimental design for 15 runs. The resulting data were empirically modelled. For each final adhesive property (i.e., loop tack, shear and peel strength), different models were found to fit the data. Similar models for loop tack and peel strength were found to be adequate for different PSA thicknesses on the same substrate. AA and SDS had significant effects on loop tack as did the AA-SDS and CTA-SDS two-factor interactions. Quadratic peel strength models were found to adequately describe the data for SS substrate cases with a noticeable absence of any interaction parameters. The shear strength models were similar regardless of the substrate or thickness of the adhesive (e.g. in all models, AA and CTA, as well as their second-order interactions, were the significant factors).