Droplet flight and solidification behaviors during twin-wire arc sprayed (TWAS) composite coatings were systematically investigated. Both theoretical model and numerical method were established for calculating the droplet deformation, breakup and solidification process in air flow based on the volume of fluid (VOF) dual-phase flow model jointed with the standard k-ε model. The experimental simulation results indicate that TWAS droplet is broken through explosion or two steps breaking process. The calculation of TWAS gas flight dynamics demonstrates that the TWAS particles are accelerated at first and then slowed down. Microstructure of the TWAS prepared Ni-5wt.%Al and Ni-20wt.%Al composite coating was accordingly characterized by XRD, SEM and TEM, so the phase compositions of the Ni-Al composite coatings were obtained. TEM analysis also showed that an amorphous phase was formed according to the characteristic of diffraction ring in Ni matrix solid solution at an original state.