Effusion cooling is one of the most effective and widespread techniques to prevent combustor liner from being damaged. However, most recent developments in combustion techniques, resulting from increasingly stricter air pollution regulations, have highlighted the necessity of reducing the amount of air available for effusion cooling while keeping an adequate level of protection. Adoption of compound angles in effusion cooling is increasingly recognized by jet engine manufacturers as a powerful solution to meet new combustor requirements. Therefore, understanding the flow behavior and developing methods able to provide accurate estimates of wall temperatures is of a major importance. This study assesses the capability of a high-level Reynolds-averaged Navier–Stokes (RANS) method, differential Reynolds stress model (DRSM), in conjunction with a generalized gradient diffusion hypothesis (GGDH), and of a hybrid RANS–large eddy simulations (LES) method, zonal detached eddy simulation (ZDES), to predict overall film effectiveness. Both approaches are compared with the experimental data from Zhang et al. (2009, “Cooling Effectiveness of Effusion Walls With Deflection Hole Angles Measured by Infrared Imaging,” Appl. Therm. Eng., 29(5), pp. 966–972) and with a classical well-known RANS model (k–ω shear-stress transport (SST) model). Despite the fact that some discrepancies are found, both approaches have proved suitable and reliable for predicting wall temperatures (relative errors of about 5%). Moreover, a new method to deal with ZDES length scales for unstructured grids is proposed. ZDES applicability and its general advantages and drawbacks are also discussed. Finally, an in-depth analysis of the film structure is carried out on the basis of the ZDES simulations. The principal structures are identified (an asymmetric main vortex (AMV) and a counter rotating vortex pair, CRVP), and the film formation mechanisms are presented. Significant spanwise-homogeneous distributions of surface overall film cooling effectiveness are observed.