In the paper, we study the plane Couette flow of a rarefied gas between two parallel infinite plates at $y=pm L$ moving relative to each other with opposite velocities $(pm alpha L,0,0)$ along the $x$-direction. Assuming that the stationary state takes the specific form of $F(y,v_x-alpha y,v_y,v_z)$ with the $x$-component of the molecular velocity sheared linearly along the $y$-direction, such steady flow is governed by a boundary value problem on a steady nonlinear Boltzmann equation driven by an external shear force under the homogeneous non-moving diffuse reflection boundary condition. In case of the Maxwell molecule collisions, we establish the existence of spatially inhomogeneous non-equilibrium stationary solutions to the steady problem for any small enough shear rate $alpha>0$ via an elaborate perturbation approach using Caflischs decomposition together with Guos $L^inftycap L^2$ theory. The result indicates the polynomial tail at large velocities for the stationary distribution. Moreover, the large time asymptotic stability of the stationary solution with an exponential convergence is also obtained and as a consequence the nonnegativity of the steady profile is justified.
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