Physically-based analytical models that provide insights into the diffusion and/or interface charge transfer effects in bulk (lithiating/delithiating) electrodes are needed to truly assess the performance/limitations of electrode materials for Li-ion batteries. In this context, an analytical modeling framework is constructed here to predict the electrochemical charge–discharge characteristics during lithiation and delithiation of solid amorphous Si (a-Si) thin film electrodes. The framework includes analytical expressions that satisfy Fick's second law for Li transport and the requisite flux boundary conditions of lithiation and delithiation steps. The expressions are derived here by the method of separation of variables. They enable the determination of transient Li concentration profiles in the thin film electrode as a function of state of charge/discharge. The time-dependent electrode surface concentrations (at the electrode–electrolyte interface) obtained from these profiles were used to determine the activation overpotentials and thus, the non-equilibrium cell potentials, as a function of state of charge/discharge using Butler–Volmer kinetics. The simulated charge/discharge characteristics agreed well with the experimental data of a-Si thin film electrodes obtained at different C-rates. The model offers insights into how the charge-discharge behavior is controlled by diffusion limitation within electrode and/or the activation overpotentials at the interface. The analytical framework is also shown to predict successfully the hysteretic behavior of lithiation/delithiation voltage curves.