Poster title: Spectropolarimetry of the scattered sunlight: from calibrations to the diagnostic of planetary atmospheres Poster abstract: It is well known that continuum twilight is highly polarised. It is much less known that the sky exhibits a wealth of spectropolarimetric features due to our atmosphere which may have a negative impact on high-accuracy polarimetric measurements. We will present some fascinating examples of low to mid-resolution spectropolarimetry of skylines obtained during twilight calibrations.