Temperature sensors may produce a measurement error of up to 1 °C because of the influence of solar radiation. In order to obtain a relatively minimal temperature error, a new temperature observation system was proposed in this paper for measuring surface air temperatures. Firstly, a radiation shield was designed with two aluminum plates, eight vents, and a multi-layer structure which is able to resist direct solar radiation, reflected radiation, and upwelling long-ware radiation, as well as ensuring the temperature sensor probe could work effectively. Then, the effect of different solar radiation intensities, wind speeds, scattered radiation intensities, long-wave radiation intensities, and underlying surface reflectivity levels on radiation error was calculated through a computational fluid dynamics (CFD) method. The mapping relationship was established between the various influencing factors and the solar radiation error. A back-propagation (BP) network algorithm was used to fit the discrete data obtained from the simulation to obtain the solar radiation error correction equation. Finally, the solar radiation error correction equation was verified. Outdoor experiments were conducted to confirm this system’s measurement accuracy. According to the experimental findings, the root-mean-square error was only 0.095 °C, which is a relatively high degree by which to reduce the temperature error. In addition, the average difference between the corrected value of the temperature observation system and the reference value was barely 0.084 °C.