The urea NOx selective catalytic reduction (SCR) is an effective technique for the reduction of NOx emitted from diesel engines. Urea spray quality has significant effect on NOx conversion efficiency. The droplet diameter and velocity distribution of air-assisted and airless urea injection systems were obtained by particle dynamics analyzer (PDA) measurement under different spray injection flow rates. It was found that the atomization quality of air-assisted urea injection system is better than that of airless urea injection system. The penetration and spray cone angle were also investigated by high-speed photography. Especially the spray characteristics of air-assisted urea injection system were measured in the constant-volume-bomb by high-speed photography. The atomization and evaporation of airless urea injection systems were modeled using computational fluid dynamics (CFD) based on the experimental results. The numerical model was validated by the experimental results. The numerical results under the different boundary conditions and injection positions of nozzles were compared in order to optimize the spray characteristics and increase the conversion efficiency of NOx.