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This paper tackles the problem of simultaneous estimation of the state and the unknown disturbance of an MIMO disturbed system and designs the disturbance rejection controller according to the estimation information. Through a series of transformations, we can transform the original system into two subsystems and then propose a sliding mode observer and a descriptor system form observer, respectively. Our algorithm can simultaneously estimate the state and the unknown disturbance. The estimation error is shown to be bounded within a small region. Moreover, the controller algorithm developed in this paper can effectively avoid the peaking phenomenon. Finally, the feasibility and the performance using the proposed method are analyzed and demonstrated with two simulated examples.