Droplet breakup and collision dynamics of an internal-mixing twin-fluid (air-assisted) spray were investigated experimentally. Time-resolved spray morphological evolutions were obtained by employing a high-speed spray visualization system, while droplet size and velocity were measured by using a phase-Doppler particle analyzer. The results show that the air-assisted spray is composed of a bulk of tiny droplets entrained by high-speed gas-phase flow. Droplets with a diameter of less than 5 µm account for the majority of samples on the basis of the distribution function. The calculated Stokes numbers of selected tracer droplets (0 µm–5 µm) show that these droplets tend to follow the air flow faithfully and thus can be used to estimate the local air flow velocity. By comparing with the critical Weber number, we found that droplet shear breakup is absent, but some droplets may undergo turbulent breakup. A theoretical analysis accounting for the effects of the turbulent dissipation rate on both droplet breakup and coalescence was performed, and the critical equilibrium length of breakup and coalescence is found to be less than 3.0 mm. In terms of droplet collision dynamics in the spray far-field, coalescence dominates droplet collision outcomes; therefore, the droplet size increases linearly as the spray downstream distance X increases. Particularly, the influence of the droplet size ratio [C. Tang, P. Zhang, and C. K. Law, “Bouncing, coalescence, and separation in head-on collision of unequal-size droplets,” Phys. Fluids 24, 022101 (2012)] was adopted to quantify the droplet coalescence probability. When compared to the n-octane spray, the n-dodecane spray accounts for more droplet bouncing (II) since n-dodecane possesses a relatively larger bouncing (II) region.