This paper presents a novel suboptimal attitude tracking controller based on the algebraic Riccati equation for a near-space hypersonic vehicle (NSHV). Since the NSHV’s attitude dynamics is complexly nonlinear, it is hard to directly construct an appropriate algebraic Riccati equation. We design the construction based on the Chebyshev series and the Koopman operator theory, which includes three steps. First, the Chebyshev series are considered to transform the error dynamics of the NSHV’s attitude into a polynomial system. Second, the Koopman operator is used to obtain a series of high-dimensional linear dynamics to approximate each of the polynomial system’s vector fields. In this step, our contribution is to determine a well-posed linear dynamics with the minimal dimension to approximate the original nonlinear vector field, which helps to design the control law and analyze the control performance. Third, based on the high-dimensional dynamics, the NSHV’s attitude error dynamics is separated into the linear part and the nonlinear part, such that the algebraic Riccati equation can be constructed according to the linear part. Then, the suboptimal error feedback control law is derived from the algebraic Riccati equation. The closed-loop control system is proved to be locally exponentially stable. Finally, the numerical simulation demonstrates the effectiveness of the suboptimal control law.