© 2016 American Chemical Society. MoS2atomic layers have recently attracted much interest because of their two-dimensional structure as well as tunable optical, electrical, and mechanical properties for next-generation electronic and electro-optical devices. Here we have achieved facile fabrication of MoS2thin films on CdS nanowires by cation exchange in solution at room temperature and importantly observed their extraordinary magnetic properties. We establish the atomic structure of the MoS2/CdS heterostructure by taking atomic images of the MoS2/CdS interface as well as performing first-principles density functional geometry optimizations and scanning transmission electron microscopy annular dark field image simulations. Furthermore, our first-principles density functional calculations for the MoS2/CdS heterostructure reveal that the magnetism in the MoS2/CdS heterostructure stems from the ferromagnetic MoS2monolayer next to the MoS2/CdS interface. The ferromagnetism is attributed to the partial occupation of the Mo dx2-y2/dxyconduction band in the interfacial MoS2monolayer caused by the mixed covalent-ionic bonding among the MoS2and CdS monolayers near the MoS2/CdS interface. These findings of the ferromagnetic MoS2monolayer with large spin polarization at the MoS2/semiconductor interface suggest a new route for fabrication of the transition metal dichalcogenide-based magnetic semiconductor multilayers for applications in spintronic devices.