An experimental study of cold-formed thin-walled steel unequal-leg angles (CFTWS-ULAs) under axially oriented pressure is presented in this paper. Firstly, the initial imperfections and material properties of the angle specimens were measured in detail. The angle specimens were tested under fixed-ended conditions. The results of the experiments showed that the angle specimens with small slenderness ratios were susceptible to local buckling, the angle specimens whose legs had high slenderness ratios and low width–thickness ratios were found to easily suffer from the occurrence of flexural buckling, and the angle specimens whose legs had high width–thickness ratios were found to easily suffer from the occurrence of interactive buckling between local buckling and flexural buckling. The finite element analysis of the ULAs was conducted using ABAQUS6.14 finite element software by creating a model. The buckling modes and ultimate bearing capacities of the test specimens were compared, and the finite element analysis verified that the established model built using the finite element is credible and subsequent parametric analysis was performed. The slenderness ratio had the most significant impact on the ultimate bearing capacities of the unequal-leg angles, as indicated by the analysis results. When the width–thickness ratio and the width ratio of the legs fell within a specific range, the ultimate bearing capacities of the unequal-leg angles increased as the width–thickness ratio and the width ratio of the legs increased. Finally, the comparison results showed that the design strengths predicted by the specifications were very conservative, because the local buckling and torsional buckling were calculated at the same time. Therefore, a recommendation was proposed that the calculation of the load-carrying capacity of an unequal-leg angle should ignore torsional buckling.