While purely numerical methods for solving ordinary differential equations (ODE), e.g., Runge–Kutta methods, are easy to implement, solvers that utilize analytical derivations of the right-hand side of the ODE, such as the Taylor series method, outperform them in many cases. Nevertheless, the Taylor series method is not well-suited for stiff problems since it is explicit and not A-stable. In our paper, we present a numerical-analytical method based on the rational approximation of the ODE solution, which is naturally A- and A(α)-stable. We describe the rational approximation method and consider issues of order, stability, and adaptive step control. Finally, through examples, we prove the superior performance of the rational approximation method when solving highly stiff problems, comparing it with the Taylor series and Runge–Kutta methods of the same accuracy order.