Composite fibers made of polyvinyl alcohol (PVA) and melamine-formaldehyde (MF) resins with different reaction degrees were prepared by wet spinning. The phase structures of MF/PVA spinning dopes and composite fibers were observed by using optical microscope (OM) and scanning electron microscope with energy-dispersive X-ray spetroscopy (SEM-EDS). Crystal structures of composite fibers were studied by X-ray diffraction (XRD) and differential scanning calorimetry (DSC). The loss of MF resins in the spinning process was calculated by using Kjeldahl. The mechanical properties, the flame retardant property, the water resistant property, and the thermal stability of composite fibers were also tested. Results show that with an increase in the reaction degree of MF resin, the phase separation degrees of spinning dopes and composite fibers rise up, the size of MF microphase grows larger, and the loss of MF resin diminishes; consequently, the hot water resistance and the flame retardancy of the fiber ameliorate while the tensile strength and the thermal stability perform a tendency of dropping after rising.