This paper deals with the recruitment schemes of enterprise knowledge workers system based on the optimal sliding mode control method. First, by considering job-transfer, natural resignation, voluntary resignation, promotion, recruitment and dismissal, the enterprise knowledge workers system can be modeled as a dynamic nonlinear uncertain system. Then, by using the optimal sliding mode control method, the design method of the optimal sliding mode control law for the system is presented. The condition for the asymptotic stability of the sliding mode manifold is proposed, and it is proved that under such a control law, the state of the enterprise knowledge workers system can reach the sliding surface in a finite time. Simulation results show that the optimal sliding mode control law (recruitment schemes) proposed in this paper can make enterprise knowledge workers system asymptotically stable. Furthermore, under the presented control law, the system is robust to parameter perturbation.