The invention belongs to the technical field of optical measurement, in particular to a multi-axial passive differential absorption spectrometry measurement system capable of recording sky conditionssimultaneously. The multi-axial passive differential absorption spectrometry measurement system capable of recording the sky conditions simultaneously comprises a rotating platform, a telescope, a camera, a central shaft, a spectrograph and a computer, wherein the telescope and the camera are respectively and vertically connected with the central shaft; the centre lines of the telescope and the camera are parallel to each other; the telescope is used for converging scattered light signals of the sun and transmitting the signals into the spectrograph; a corresponding spectrogram is obtained after the signals are subjected to light splitting through the spectrograph; the spectrogram is input into the computer; the camera is used for shooting sky cloud layer pictures and inputting the sky cloud layer pictures into the computer; the computer controls the rotating angle of the central shaft by controlling the rotating platform, so that the telescope and the camera are controlled to acquirespectral signals and sky cloud layer conditions at any angle simultaneously; the computer analyses spectral information to obtain the column concentration of trace pollutants in a troposphere; the vertical distribution information of the pollutants when the cloud layer interference is low is acquired by combining the shot sky cloud layer pictures.