- A new nanometric cubic binary phase of the tin mono-selenide system, π-SnSe, was obtained as cube shaped nanoparticles. Its structure and atomic positions were adopted from previously reported π-SnS (P213, a0 = 11.7 Å). The proposed structure model of π-SnSe, with 64 atoms per unit cell, was refiend against experimental X-ray diffraction using Rietveld method (a0 = 11.9702(9) Å; Rp= 1.65 Rwp= 2.11). The optical properties of this new cubic SnSe phase were characterized by Raman and optical absorption spectroscopies. The optical band gap was assessed to be indirect, with Eg=1.28 eV (in the near infrared), compared to Eg=0.9 eV (indirect) and 1.3 eV (direct) for the conventional orthorhombic phase of α-SnSe. Raman spectroscopy indicated significant phonon restraining, which is likely to be beneficial for thermoelectric applications. Since the new cubic phase belongs to a class of non-centrosymmetric crystals, interesting and potentially useful piezoelectric properties can be expected. Density functional theory calculations have been applied in order to validate phase stability and evaluate the energy bandgap. These results, together with the recently discovered cubic phase of π-SnS, confirm the existence of a new class of nanoscale materials in the tin chalcogenide system.