This study investigates the structural and electronic properties of BiSbPbTe thin films, focusing on the impact of post-annealing time and temperature. The X-ray diffraction (XRD) analysis reveals a stable rhombohedral phase formation in all samples, with no secondary phases detected within the detection limit. The high crystallinity of the films is confirmed, and post-annealing leads to an increase in peak intensity, indicating enhanced crystalline structure. Surface morphology analysis using scanning electron microscopy (SEM) demonstrates a transition from inhomogeneous features in as-grown films to homogeneous and dense formations in post-annealed films. The grain size increases with post-annealing time, attributed to diffusion, energy minimization, nucleation, growth, and thermal activation processes. The electronic transport properties, including carrier concentration and conductivity, are influenced by post-annealing temperature and duration. A stable carrier concentration is observed for films post-annealed for up to 2 h, while longer durations decrease due to reduced defect vacancies and grain boundaries. The increase in charge carrier mobility, confirmed by SEM results, contributes to enhanced electrical conductivity. The Seebeck coefficient shows an initial enhancement up to 2 h post-annealing, attributed to defect creation and increased grain boundaries. However, further increases in post-annealing duration result in a decrease in the Seebeck coefficient due to enhanced charge carrier mobility and reduced grain boundaries. The thermoelectric power factor (4.4 μW/cm1K2), determined by the square of the Seebeck coefficient and electrical conductivity, reaches its maximum value in the 2-h post-annealed sample, emphasizing the importance of optimizing post-annealing conditions for improved thermoelectric performance.