Abstract This work investigates the correlation between the formulation of waterborne acrylic pressure‐sensitive adhesives (PSAs) and their resulting adhesive performance. A library of n ‐butyl acrylate‐based latexes is synthesized via miniemulsion polymerization. Controlled variations in the composition of these polyacrylates – such as the inclusion of rigid comonomers, latent crosslinkers and chain transfer agents – enabled precise control over key network structures in the particles leading then to a range of physical parameters in the cast PSA films such as the glass transition temperature, entanglement and crosslink density. The viscoelastic and mechanical behaviors of the resulting networks are carefully characterized using a combination of techniques, including linear rheology, dynamic mechanical analysis, and tensile testing. These properties are then correlated with adhesive performance, as measured by probe tack and shear holding time tests. This comprehensive approach allowed for the identification of the optimal formulation balance that delivers the best compromises of adhesive performance, directly correlating these outcomes with the macromolecular design.