We present a detailed analysis of GRB 151006A, the first GRB detected by Astrosat CZT Imager (CZTI). We study the long term spectral evolution by exploiting the capabilities of Fermi and Swift satellites at different phases, which is complemented by the polarization measurement with the CZTI. While the light curve of the GRB in different energy bands show a simple pulse profile, the spectrum shows an unusual evolution. The first phase exhibits a hard-to-soft (HTS) evolution until ∼ 16 − 20 s, followed by a sudden increase in the spectral peak reaching a few MeV. Such a dramatic change in the spectral evolution in case of a single pulse burst is reported for the first time. This is captured by all models we used namely, Band function, Blackbody+Band and two blackbodies+power law. Interestingly, the Fermi Large Area Telescope (LAT) also detects its first photon (> 100 MeV) during this time. This new injection of energy may be associated with either the beginning of afterglow phase, or a second hard pulse of the prompt emission itself which, however, is not seen in the otherwise smooth pulse profile. By constructing Bayesian blocks and studying the hardness evolution we find a good evidence for a second hard pulse. The Swift data at late epochs (> T 90 of the GRB) also shows a significant spectral evolution consistent with the early second phase. The CZTI data (100-350 keV), though having low significance (1σ), show high values of polarization in the two epochs (77% to 94%), in agreement with our interpretation.