The charge exchange and the energy transfer between Earth's upper atmosphere and high-energy electrons play an important role in the upper atmospheric luminous phenomena such as aurora and airglow. By building a ground-based simulating setup for electron excited high-altitude atmospheric radiation based on a vacuum system, the ionizing excitation of neutral molecules induced by electron impact and the corresponding radiative transition mechanism in the upper atmosphere are verified here. The device can create a vacuum gradients of more than 5 orders from 10² to 10^-3 Pa, generate electrons with kinetic energy in 10²-10³ eV and monitor spectral transitions with wide range from near ultraviolet to near infrared. As an illustrated example, the setup has been applied to study the electron excitation of N₂ and O₂, the two main components of atmosphere, and their spectral distributions are measured and compared. It's found that the emission spectral intensity of N₂ is not only positively correlated with electron energy, but also much higher than that of O₂ under the same condition. Using the known spectral bands of the pure gases of N₂ and O₂, the excited spectrum of the actual atmosphere has been assigned, which shows that the emission bands of the air and pure N₂ tend to be convergent, but the former's intensity decreases in some contents. These results demonstrate that the developed setup can be used to simulate the colliding excitation of middle and upper atmosphere components during the deposition of high-energy electrons.