A protective cover structure includes a main body with an accepting space to form a frame structure. A lid engages with the main body at the bottom of the frame through corresponding buckling elements. A groove is respectively disposed on the peripheries of upper and lower surfaces of the main body, where the groove of the lower surface is used for coupling and securing a decorative bottom plate, and the groove of the upper surface couples with an annular decorative body. In use, a user first removes the lid from the main body, inserts an electronic device, and then tightly covers the lid onto the main body, thereby securely receiving the electronic device in the main body to protect the electronic device, and providing decorative effects through the configurations of the decorative bottom plate and decorative body.