The field of valleytronics has promised greater control of electronic and spintronic systems with an additional valley degree of freedom. However, conventional and two-dimensional valleytronic systems pose practical challenges in the utilization of this valley degree of freedom. Here we show experimental evidences of the valley effect in a bulk, ambient, and bias-free model system of Tin(II) sulfide. We elucidate the direct access and identification of different sets of valleys, based primarily on the selectivity in absorption and emission of linearly polarized light by optical reflection/transmission and photoluminescence measurements, and demonstrate strong optical dichroic anisotropy of up to 600% and nominal polarization degrees of up to 96% for the two valleys with band-gap values 1.28 and 1.48 eV, respectively; the ease of valley selection further manifested in their non-degenerate nature. Such discovery enables a new platform for better access and control of valley polarization.