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In order to make the most of solar energy, the development of efficient UV–Vis–NIR activated photocatalysts has attracted more and more attention. In this study, the UV–Vis–NIR broad spectrum activated photocatalysts La-doped BaBiO 2 Cl with abundant oxygen vacancies (OVs) were successfully prepared by solid state reaction. The experimental results and theoretical calculations revealed that La doping induced OVs in BaBiO 2 Cl, formed an intermediate level, extended the light absorption to the NIR region, and promoted carrier separation efficiency. Owing to the synergistic promotion effect, the optimal BaBiO 2 Cl–3%La exhibited obviously enhanced photodegradation rate, which was about 3.26 times higher than that of pure BaBiO 2 Cl under UV–Vis–NIR light irradiation. This work provides a resultful strategy for designing new full-spectrum-activated photocatalysts for environmental protection. The UV–Vis–NIR activated photocatalysts La-doped BaBiO 2 Cl with abundant OVs were successfully prepared by solid state reaction. Theoretical calculations and experimental results revealed that La doping induced OVs in BaBiO 2 Cl, formed an intermediate level, extended the photoresponse to the NIR region, and promoted carrier separation efficiency, resulting in enhancing overall photocatalytic activity under UV–Vis–NIR light irradiation. [Display omitted] • La doping induced the formation of abundant oxygen vacancies in BaBiO 2 Cl. • La-doped BaBiO 2 Cl with oxygen vacancies exhibited high photocatalytic activity under UV–Vis–NIR light irradiation. • Both theoretical calculations and experimental measurements reveal the enhanced mechanism. • The enhanced photocatalytic activity is ascribed to the introduction of La and oxygen vacancies. [ABSTRACT FROM AUTHOR]