Spherical silicon (Si) with a size of ∼1mm diameter was fabricated by the dropping method for the applications of spherical Si solar cells. In this research work, we characterized spherical Si by means of photoluminescence (PL) measurement at 4 and 18K. The horn-type spherical Si crystals, formed under large undercooled conditions without a seeding technique, showed D-band luminescence originating from dislocations, whereas intrinsic PL bands of Si were not observed. In contrast, for the tear-type spherical Si crystals, formed under shadow undercooling by a seeding technique with Si powder, the boron (B) bound and Si intrinsic phonon-assisted PL bands were clearly observed both at 4 and 18K. Moreover, the intensity ratio of B bound exciton band to Si intrinsic phonon-assisted PL band showed good correlation to the minority carrier lifetime measured with microwave photoconductance decay method. These experimental results suggested that the crystallinity of the tear-type spherical Si is significantly improved by the seeding technique compared with the horn-type ones, which contain a large amount of B-related defects.