Novel　Eu,　F-codoped　BiVO4microspheres　with　diameter　of　1–3　μm　were　successfully　fabricated　via　a　hydrothermal　route.　The　effects　of　Eu　and　F　doping　on　the　morphology　and　crystal　structure　were　intensively　investigated　by　some　physicochemical　characterizations　like　N2physical　adsorption,　X-ray　diffraction　(XRD),　Scanning　electron　microscope　(SEM),　Transmission　electron　microscopy　(TEM),　UV–Vis　diffuse　reflectance　(UV–vis　DRS),　X-ray　photoelectron　spectroscopy　(XPS)　and　photoelectrochemical　measurements.　The　characterization　results　revealed　that　the　doping　of　Eu3+induced　the　formation　of　BiVO4microspheres　and　the　phase　transformation　in　BiVO4crystal,　from　monoclinic　to　tetragonal　phase.　The　Eu3+doping　slightly　shifted　the　absorption　edge　of　BiVO4to　the　direction　of　UV　region.　F−doping　clearly　increased　the　crystallinity　of　BiVO4.　Moreover,　Eu　and　F　co-doping　gave　rise　to　the　synergetic　effects,　e.g.　the　increase　in　surface　area　and　high　separation　efficiency　of　the　photo-generated　electrons　(e−)　and　holes　(h+).　The　photocatalytic　performance　test　in　degradation　of　rhodamine　B　showed　that　these　Eu,　F-codoped　BiVO4microspheres　displayed　much　higher　photocatalytic　performance　than　that　of　bare　BiVO4,　single　Eu　or　F　doped　BiVO4samples.　©　2016　Elsevier　B.V.