Cable-stiffened steel columns (CSSC) have a high load-carrying capacity and strong stability compared to ordinary steel columns. In practical engineering, the connection between the crossarm and main column of a CSSC is usually welded. However, the welding-residual stress adversely affects the steel column. In this study, pre-cast CSSCs, with a pinned connection between the crossarm and main column, are presented. The new type of pre-cast CSSCs avoid the welding-residual and are easy to disassemble. A model test and numerical analysis of its global stability behavior under eccentric compression is conducted. Based on the analysis, the buckling modes of these columns are defined and a method for determining the governing imperfection in a nonlinear buckling analysis is proposed. The effects of slenderness ratio, cross-arm length, cable diameter, and other parameters on the load-carrying capacities of the columns are investigated using the proposed method. The results of this study can be used as a reference for the engineering designs and specifications of pre-cast CSSCs.