Rhodopseudomonas palustris immobilized on multiple materials was used to invistigate Cr(VI) adsorption and bioreduction. The highest Cr(VI) removal (97.5%) was achieved at 276h under the opitimed conditions of 2.5% SA, 8% PVA, and 50% filling degree. The highest adsorption capacity was obtained at 11.75 mg g−1 under 300 mg L−1 Cr(VI). Results from adsorption kinetics and isotherms indicated that Cr(VI) adsorption of immobilized photosynthetic bacteria (IPSB) was consistent with the Freundich model and the pseudo-second-order kinetic model (qe = 14.00 mg g−1). SEM and FTIR analyses verified that the porous multilayer network structure of IPSB provided more adsorption sites and functional groups for the removal of Cr(VI). Furthermore, the maximum Cr(VI) reduction efficiency of IPSB was achieved at 10.80 mg g−1, which correlated with the up-regulation of chrR gene expressions at 100 mg L−1 Cr(VI). This study demonstrated the dual mechanisms of Cr(VI) removal in IPSB-treated Cr wastewater, involving both chemisorption and bioreduction working synergistically.