In　this　work,　a　complex　impedance　spectroscopy　study　of　bismuth　vanadate　(BiVO4)　ceramics　with　different　additions　of　ZnO　(25,　50,　and　75 wt %)　was　performed.　BiVO4　(BVO)　was　synthesized　by　the　reaction　method　in　solid-state　and　calcined　at　500 °C　and　BVO–ZnO　composites　were　moulded　in　sintered　ceramic　pellets　at　700 °C.　X-ray　diffraction　(XRD)　was　used　to　analyse　the　crystal　structure　of　BVO　and　the　BVO–ZnO　composites;　none　spurious　phase　was　observed　during　the　synthesis.　Analysis　by　complex　impedance　spectroscopy　(CIS)　showed　that　increasing　the　concentration　of　ZnO　reveals　increased　activation　energy　due　to　thermo-activated　charge　transfer　for　the　sample　with　25　wt %　ZnO.　At　room　temperature,　the　increase　in　the　ZnO　concentration　in　the　BVO　matrix　maintained　a　high　value　for　the　dielectric　constant　(Ε),　in　the　order　of　104　at　a　frequency　of　1 Hz.　Average　normalized　change　(ANC)　was　used　to　identify　the　temperature　at　which　the　available　density　of　trapped　charge　states　vanishes　in　each　sample.　The　temperature　coefficient　of　capacitance　was　positive　for　BVO　and　negative　for　composites.　The　adjustment　through　the　equivalent　circuit　presented　excellent　electrical　response　for　the　composites,　and　identified　an　association　with　three　resistors,　each　in　parallel　a　constant　phase　element,　showing　the　influence　of　grain　and　grain　boundary　on　the　process　of　thermo-active　conduction.　©　2020,　Springer　Science+Business　Media,　LLC,　part　of　Springer　Nature.