It is very difficult to observe the celestial bodies in the daytime. The methods of spectro-polarimetric imaging and the skylight polarization measurements in real-time are adopted to largely reduce influence of atmospheric scattering. The SNR and contrast of celestial bodies detection in the skylight background are enhanced. The principle of spectro-polarimetric imaging for the celestial bodies detection in the severely atmospheric scattering was discussed. The related experimental system was introduced. The experimental measurements of spectro-polarimetric imaging for the stars were performed. The 6.33^m star can be measured using spectro-polarimetric imaging in the daytime. This result of experiments was compared with that of spectral imaging. The results indicate that the contrast of celestial bodies detection using spectro-polarimetric imaging is enhanced obviously. Hence, it shows that the technique of spectro-polarimetric imaging can be applied to the research of celestial bodies observation in the daytime.