AbstractMössbauerdata recorded at room temperature and 78 K for several binary and two new ternary vanadium sulfides are presented. The results are discussed in comparison with the structures and magnetic susceptibility measurements. A change in the spin state of the Fe‐atoms from the Fe2+high‐spin state to the low‐spin state is observed in the binary vanadium sulfides. This change is due to a shortening of the crystallographicc‐axis which is nearly parallel to short metal‐metal distances. In one ternary thallium vanadium sulfide the Fe is in the unusual trivalent low‐spin state at room