Using introduction of MoO₄²⁻ and Fe³⁺, Cu²⁺, or Zn²⁺ into amphiphilic polymers (DN) via an ion-exchange reaction, different transition metal complexes, as retardants and smoke suppressants, including (DN)Mo, Fe(DN)Mo, Cu(DN)Mo, and Zn(DN)Mo were synthesized. Combined with the results of X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD), and Fourier transform infrared spectroscopy (FTIR), it could be determined that ionic bonding of these ions with DN occurred. Subsequently, the influence of flame-retardant, smoke-suppression, and mechanical properties of (DN)Mo, Fe(DN)Mo, Cu(DN)Mo, and Zn(DN)Mo on polyvinyl Chloride (PVC) were tested. It was demonstrated that transition metal complexes of three metal elements, Fe(DN)Mo, Cu(DN)Mo, and Zn(DN)Mo, showed better flame retardancy, smoke suppression, and thermal stability as confirmed by microcalorimetry, limiting oxygen index (LOI), smoke density, and thermogravimetric analysis (TGA) tests, in which Cu(DN)Mo worked best due to the Lewis acid mechanism and reductive coupling mechanism. Scanning electron microscopy (SEM) showed that the addition of (DN)Mo, Fe(DN)Mo, Cu(DN)Mo, and Zn(DN)Mo promoted the formation of a dense carbon layer on the PVC surface during combustion, which could protect the interior PVC. The addition of these transition metal complexes hardly impaired the mechanical properties of PVC.