This paper focuses on the behavioral modeling of the passive RF blocks from frequency-domain samples. This work is based on vector fitting (VF) approach which is a robust method for MIMO system identification in the frequency domain. This paper addresses firstly the problem of convergence using envelope transient (ET) on complex circuits, i.e. power amplifiers (PAs), where linear sub-circuits are widely described through S-parameters matrices derived from ElectroMagnetic (EM) simulations. An alternative way leads to combine VF method with an RLC synthesis process at the circuit level. This approach is validated on a simple circuit case and generalized to MIMO systems. Second application is the behavioral modeling of MIMO blocks at system level in a high-level spice-like system simulation tool which allows “Control Flow” simulations. The proposed approach combines on one hand the VF method with and impulse responses evaluation on the other hand. In consequence, bilateral behavioral models of MIMO system can be efficiently achieved irrespective of the number of access. This method is validated at once on simple and complex MIMO blocks. As a result, the topological behavioral modeling of complex PAs, which distinguish linear sub-circuits and nonlinear ones, is now possible in a high-level time-domain CAD tool.