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High-entropy perovskite thin films, as the prototypical representative of the high-entropy oxides with novel electrical and magnetic features, have recently attracted great attention. Here, we reported the electronic structure and charge transport properties of sol-gel-derived high-entropy Ba(Zr 0.2 Sn 0.2 Ti 0.2 Hf 0.2 Nb 0.2)O 3 thin films annealed at various temperatures. By means of X-ray photoelectron spectroscopy and absorption spectrum, it is found that the conduction-band-minimum shifts downward and the valence-band-maximum shifts upward with the increase of annealing temperature, leading to the narrowed band gap. Electrical resistance measurements confirmed a semiconductor-like behavior for all the thin films. Two charge transport mechanisms, i.e. , the thermally-activated transport mechanism at high temperatures and the activation-less transport mechanism at low temperatures, are identified by a self-consistent analysis method. These findings provide a critical insight into the electronic band structure and charge transport behavior of Ba(Zr 0.2 Sn 0.2 Ti 0.2 Hf 0.2 Nb 0.2)O 3 , validating it as a compelling high-entropy oxide material for future electronic/energy-related technologies. [ABSTRACT FROM AUTHOR]