The transient Couette flow problem of rarefied binary gas mixtures is studied for the nonlinear case, Mi ≥ 1: one of the plates with equal plate temperatures is accelerated impulsively. The method of solution is the Monte Carlo method. The physical space is divided into macroscopically small cells. The change in the distribution function in a cell during a time interval Δt, which should be sufficiently small in comparison with the characteristic times (τD)iα, (τF)iα, and (τC)ij, is obtained by following the test particles for each molecular event through the event; i.e., molecular drift, external force, or molecular collision. The flow field is calculated for Maxwellian molecules and the range of Knudsen number Kn ≥ 0.1 (from free molecular to transition flow regime). The relaxation phenomena of a gas mixture with the boundary effects are observed. Of particular interest are an epochal relaxation due to the molecule-surface collision and the temperature “overshoot” near the moving plate. The steady-state solutions, which are obtained from the long-time results, are also presented. The effects of Knudsen number, mixture ratio, and gas-surface interaction are investigated, and the separation phenomena between the species are observed.