This work explores technical challenges and potential methodologies for understanding electrochemical Reactive CO2 Capture (RCC) mechanisms. RCC offers potential energy cost advantages by directly converting captured CO ₂ into fuels and chemicals, unlike traditional carbon capture and utilization (CCU) processes that require sequential capture, concentration, and compression. However, direct conversion of captured CO ₂ introduces complexity due to additional equilibrium buffer reactions, making it challenging to identify active species for reduction in electrochemical studies. This work discusses methods to integrate transport, thermodynamics, and kinetics concepts to identify active carbon sources in RCC. Vapor-Liquid Equilibrium (VLE) and transport models are validated against experimental results obtained in a gastight rotating cylinder electrode reactor and are shown as useful tools for studying RCC in heterogeneous electrocatalysts across different capture agents, solvents, and temperatures. This work establishes an experimental framework for advancing research in electrochemical RCC.