Diagnostics of particles produced from Value-Arc 100 twin-wire-arc spraying system was found using DPV2000 monitoring tool. Effect of different operating parameters on the diagnostics of the particles, namely, temperature, velocity, and size distributions, were experimentally studied and discussed. It was found that the particle characteristics are not symmetric about the center line of the plume. It was also found that the divergence angle in the plane parallel to both wires is less than the divergence angle in the symmetry plane of the wires, which is observed in the actual oval-shape coating structure and is explained by the geometry of the system. Size distribution and volumetric size distribution of particles are also analyzed and compared with log-normal distribution function. It is shown that the size distribution consists of two different peaks believed to be associated with anodic and cathodic particles in the process.