We propose time-resolved specular neutron reflectivity (NR) measurements during electrodeposition of polyaniline (PAni) films via different electrochemical control functions: potentiostatic (PS), potentiodynamic (PD) and galvanostatic (GS). Motivation is provided by a huge literature on this process and material that reports widely divergent properties and performance - without underlying structural or compositional rationale - which inhibits optimization for device fabrication. We explore the concept that different electrochemical control functions generate films of different solvent content that, through viscosity effects, lead to variations in ion (¿dopant¿) transport rate and polymer chain dynamics. These in turn control device switching rate, mechanical stability and longevity.