The spray mixing process can be improved via straight (ST) duct fuel injection, but there is a risk of potential heat transfer loss due to prolonged spray tip penetration (STP) and spray impingement. We proposed a convergent-divergent (CD) duct spray to produce an acceptable STP along with improved spray air entrainment and spray cone angle (SCA), which is validated in optical spray experiments. How the CD duct enhances the fuel–air mixing and why the spray left–right swing phenomenon occurs near the outlet of the CD duct is still unknown. This study focuses on the spray mixing process inside CD and ST ducts using large eddy simulations. Results showed that the larger vortex cluster is formed in the divergent outlet with the large diameter of 4.5 mm and 6 mm, named CD4.5 and CD6 ducts, which leads to the unstable fluctuations of the separated shear flow and a large number of vortex shedding from the inner wall of the CD duct outlet to promote the radial fuel–air mixing with the left–right swing phenomenon, which further enlarges the SCA and appropriately shortens the STP with reduced spray energy. Compare to free spray, there are two turbulence kinetic energy (TKE) peaks in the spray axial centerline, indicating that duct spray brings extra disturbance to spray and is conducive to promoting the fuel–air mixing process. The strongest TKE region appears near the outlet of CD4.5 and CD6 duct sprays that are consistent with the left–right spray swing motion phenomenon.