Creating allotropes and polymorphs of nanoparticles (NPs) has gained tremendous momentum in recent times. Group 14 (C, Si, Ge) has a number of allotropes; some with significant applications. Here we report the synthesis of Si NPs crystallizing in the BC8 structure via a colloidal route for the first time. The BC8 structure is a metastable structure of Si that can be accessed from the β-Sn form through the release of high pressure. These Si BC8 structured NPs were synthesized via reduction of SiI4 with n-butyllithium, capped with octanol and precipitated from solution. The transmission electron microscopy lattice fringes as well as the selected area electron diffraction pattern of the precipitate are consistent with the BC8 structure. The LeBail whole profile fitting of powder X-ray diffraction data also confirms the structure as the BC8 phase. The Raman spectrum provides further evidence to support the BC8 structure. With proper tuning of the band gap these NPs could be potential candidates for solar cells.