The Shangling vanadium deposit, which occurs in the Lower Devonian Tangding formation black rock series strata, has V2O5 reserves of more than 1.5 million tons and prospective reserves of more than 2 million tons. Preliminary studies on the occurrence state of vanadium(V) in this deposit have been conducted by artificial heavy minerals concentrates, leaching experiments, scanning and transmission electron microscopy and X-ray powder diffraction.These experiments have revealed no independent vanadium mineral occurrences in the Shangling vanadium deposit and the percentages of water-soluble vanadium, hydrochloric acid soluble vanadium and HF soluble vanadium were1.93 %, 21.42 % and 76.47 %, respectively. Based on our data and earlier research, we estimate that the valences state of V absorbed onto the surface of organic matter or clastic particles are +5 and +4, accounting for 10.00 % and13.35 % of the total amount of V, respectively and the valences state of V that exist in the octahedral crystal lattice of authigenic illite include +3 and +4, accounting for71.64 % and 4.83 % of the total amount of V, respectively.By calculating the correlation between the total organic carbon and V, we infer that after deposition and before entering the crystal lattice of illite, V occurs in the form of humate complex or is adsorbed by organic matter. About4.24 % of the Al is in the octahedral crystal lattice of illite,which was replaced by the vanadium under the metallogenic environments of Shanglin. The Shangling vanadium deposit, which occurs in the Lower Devonian Tangding formation black rock series strata, has V2O5 reserves of more than 1.5 million tons and prospective reserves of more than 2 million tons. Preliminary studies on the occurrence state of vanadium (V) in this deposit have been conducted by artificial heavy minerals concentrates, leaching experiments, scanning and transmission electron microscopy and X-ray powder diffraction. these experiments have revealed no independent vanadium mineral occurrences in the Shangling vanadium deposit and the percent percent of water-soluble vanadium, hydrochloric acid Based on our data and earlier research, we estimate that the valences state of V absorbed onto the surface of organic matter or clastic particles are +5 and + 4, accounting for 10.00% and13.35% of the total amount of V, respectively and the valences state of V that exist in the octahedr al crystal lattice of authigenic illite include +3 and +4, accounting for71.64% and 4.83% of the total amount of V, respectively.By calculating the correlation between the total organic carbon and V, we infer that after deposition and before entering the crystal lattice of illite, V occurs in the form of humate complex or is adsorbed by organic matter. About 4.24% of the Al is in the octahedral crystal lattice of illite, which was replaced by the vanadium under the metallogenic environments of Shanglin.