The simultaneous interception of multiple exo-atmospheric threat targets can leave no buffer time for the targets and greatly reduces targets’ penetration probability. This paper proposes centralized and decentralized two midcourse guidance methods to solve the coordinated interception of multiple exo-atmospheric targets. First, the free-time cooperative interception problem minimizing the total impulses is established, where the nonlinear dynamics of the interceptors and targets, the initial impulse constraints, and the terminal interception constraints are considered. Second, the necessary conditions for the optimal cooperative interception problem are derived and then approximated using higher-order Taylor expansions, which result in a series of analytical nonlinear equations. Then, the semi-analytical centralized guidance mode is designed to achieve simultaneous interception of targets by directly solving the analytical nonlinear equations. To improve computational efficiency, the decentralized cooperative guidance mode is further proposed by using the developed iterative freezing trajectory method, where each interceptor uses information from other interceptors in the previous iteration for prediction and distributed computation. Numerical examples verify the effectiveness and robustness of the proposed two guidance methods. Results show that the computational efficiency of the decentralized guidance mode is more efficient compared with the centralized midcourse guidance mode.