A nickel hydroxide/carbon black/polyvinylidene fluoride (Ni(OH)2/CB/PVDF) film was coated on a graphite plate substrate and used for the selective and efficient extraction of W(VI) using self-driven film adsorption. The excellent self-driven adsorption performance of Ni(OH)2/CB/PVDF film for W(VI) was demonstrated by the comparison of the experimental performance of film adsorption and electrochemically switched ion exchange (ESIX) process. In the Ni(OH)2/CB/PVDF film, the adsorption of W(VI) by Ni(OH)2 was achieved through the ligand exchange reaction with W(VI) and abundant hydroxyl groups, which ensured the self-driven performance. The adsorption capacity of the self-driven Ni(OH)2/CB/PVDF film for W(VI) under neutral conditions could reach up to 37.53 mg·g−1 after 12 h. Moreover, the adsorption kinetics and adsorption thermodynamics showed that the adsorption of W(VI) on Ni(OH)2/CB/PVDF films was more in line with the pseudo-second-order kinetic model, and the adsorption was heat-absorbing and spontaneous. After seven cycles of adsorption/desorption, the adsorption capacity of W(VI) by Ni(OH)2/CB/PVDF film could reach 79.37 % of its initial value, which showed good adsorption/desorption cycle performance. Moreover, Ni(OH)2/CB/PVDF films showed high selectivity for W(VI) when WO42− coexisted with Cl−, NO3–, and SO42−, respectively. This study confirmed that the self-driven Ni(OH)2/CB/PVDF film had efficient and stable adsorption performance for W(VI), which can be regarded as a promising method for the selective adsorption of W(VI) from aqueous solution.