Ground-based observations of zenith sky polarisation have been performed with the GOME Breadboard Model. This spectrometer operates at high spectral resolution (0.2 - 0.4 nm) while at the same time covering a broad spectral range from the UV into the near-IR (300 - 790 nm). Spectral fine-structures have been observed in the zenith sky polarisation which are related to the Ring effect and to molecular absorption in the atmosphere. First results obtained on a clear sky day are presented.