Context. Earthshine, i.e. sun-light scattered by Earth and back-reflected from the lunar surface to Earth, allows observations of Earth's total flux and polarization with ground-based astronomical facilities on timescales from minutes to years. Like flux spectra, polarization spectra exhibit imprints of Earth's atmospheric and surface properties. Earth's polarization spectra may prove an important benchmark to constrain expected bio-signatures of Earth-like planets observed with future telescopes. Aims. We derive Earth's polarimetric phase curve from a statistically significant sample of Earthshine polarization spectra. The impact of changing Earth views on the variation of polarization spectra is investigated. Methods. We present a comprehensive set of spectropolarimetric observations of Earthshine as obtained by FORS2 at the VLT for phase angles from 50 • to 135 • (Sun-Earth-Moon angle), covering a spectral range from 4300Å to 9200Å. The degree of polarization in B, V, R, I passbands, the differential polarization vegetation index, and the equivalent width of the O 2 -A polarization band around 7600Å are determined with absolute errors around 0.1% in the degree of polarization. Earthshine polarization spectra are corrected for the effect of depolarization introduced by backscattering on the lunar surface, introducing systematic errors of the order of 1% in the degree of polarization. Results. Distinct viewing sceneries such as observing the Atlantic or Pacific side in Earthshine yield statistically different phase curves. The equivalent width defined for the O 2 -A band polarization is found to vary from -50Å to +20Å. A differential polarized vegetation index is introduced and reveals a larger vegetation signal for those viewing sceneries that contain larger fractions of vegetated surface areas. We corroborate the observed correlations with theoretical models from the literature, and conclude that the Vegetation Red Edge (VRE) is a robust and sensitive signature in polarization spectra of planet Earth. Conclusions. The overall behaviour of polarization of planet Earth in the continuum and in the O 2 -A band can be explained by existing models. Bio-signatures such as the O 2 -A band and the VRE are detectable in Earthshine polarization with a high degree of significance and sensitivity. An in-depth understanding of Earthshine's temporal and spectral variability requires improved models of Earth's biosphere, as a pre-requisite to interpret possible detections of polarised bio-signatures in Earth-like exoplanets in the future.