Inertial-based navigation refers to the navigation methods or systems that have inertial information or sensors as the core part and integrate a spectrum of other kinds of sensors for enhanced performance. Through a series of papers, the authors attempt to explore information blending of inertial-based navigation by a polynomial optimization method. The basic idea is to model rigid motions as finite-order polynomials and then attacks the involved navigation problems by optimally solving their coefficients, taking into considerations the constraints posed by inertial sensors and others. In the current paper, a continuous-time attitude estimation approach is proposed, which transforms the attitude estimation into a constant parameter determination problem by the polynomial optimization. Specifically, the continuous attitude is first approximated by a Chebyshev polynomial, of which the unknown Chebyshev coefficients are determined by minimizing the weighted residuals of initial conditions, dynamics and measurements. We apply the derived estimator to the attitude estimation with the magnetic and inertial sensors. Simulation and field tests show that the estimator has much better stability and faster convergence than the traditional extended Kalman filter does, especially in the challenging large initial state error scenarios.