Consider a class of coupled Stein equations arising from jump control systems. An operator Smith algorithm is proposed for calculating the solution of the system. Convergence of the algorithm is established under certain conditions. For large-scale systems, the operator Smith algorithm is extended to a low-rank structured format, and the error of the algorithm is analyzed. Numerical experiments demonstrate that the operator Smith iteration outperforms existing linearly convergent iterative methods in terms of computation time and accuracy. The low-rank structured iterative format is highly effective in approximating the solutions of large-scale structured problems.