Parameter estimation is an important step in the identification of systems. With the extension of systems, there needs the multi-parameter estimation of systems. The estimation of multi parameters of complex systems based on the extended PID controllers is considered in this chapter. As the related references proved that the integral item of the nonlinear PID controller could deal with the uncertain part of the complex system (which can also be called new stripping principle, simple notes as NSP). Based on this theory, new multi-parameter estimation method is given. Firstly, the unknown parameters are expanded to new states of the system. Two cases, parameters are constant or changing with time, are separately analyzed. In the time-variant case, the unknown parameters are extended to functions which actual forms are uncertain. Secondly the method NSP could be applied to cope with the uncertain part, and then reconstruction state observation to estimate the states. If the states are observed, the unknown parameters are obtained at the same time. Finally the convergence analysis of the error systems and some simulations will be given in this chapter to indicate the effectiveness of the proposed method.