The excited states of 209Po have been investigated via the 208Pb(α, 3n)209Po reaction, at a beam energy of 40 MeV delivered by the K-130 Cyclotron at VECC, Kolkata. The de-excited γ-rays were detected with the Compton-suppressed Clover HPGe detectors of the Indian National Gamma Array (INGA) setup. The level scheme has been significantly extended by identifying and placement of 63 new γ-ray transitions. The spin-parity assignments of the different levels have been carried out on the basis of directional correlation of oriented states and polarization asymmetry measurements. Additionally, the possible presence of an isomeric state at a spin of 23/2+ has been indicated. Large Scale Shell Model calculations have been performed, with the inclusion of excitations of neutrons across the N = 126 core, and compared with the experimental results.