The high-order compact finite difference technique is introduced to solve the Boltzmann model equation, and the gas-kinetic high-order schemes are developed to simulate the different kinetic model equations such as the BGK model, the Shakhov model and the Ellipsoidal Statistical (ES) model in this paper. The methods are tested for the one-dimensional unsteady shock-tube problems with various Knudsen numbers, the inner flows of normal shock wave for different Mach numbers, and the two-dimensional flows past a circular cylinder and a NACA 002 airfoil to verify the reliability of the present high-order algorithm and simulate gas transport phenomena covering various flow regimes. The computed results are found in good agreement both with the theoretical prediction from continuum to rarefied gas dynamics, the related DSMC solutions, and with the experimental results. The numerical effect of the schemes with the different precision and the different types of Boltzmann collision models on the computational efficiency and computed results is investigated and analyzed. The numerical experience indicates that an approach developing and applying the gas-kinetic high-order algorithm is feasible for directly solving the Boltzmann model equation.Boltzmann model equation, velocity distribution function, high-order compact scheme, discrete velocity ordinate method, gas-kinetic high order accurate algorithm