Cadmium selenide is a II−VI semiconductor model system known for its nanoparticle preparation, growth mechanism, luminescence properties, and quantum confinement studies. For the past 2 decades, various thermodynamically stable "magic-size nanoclusters (MSCs)" of CdSe have been observed, isolated, and theoretically calculated. Nevertheless, none of the proposed structures were experimentally confirmed due to the small crystal domains beyond the diffraction limit. With a combination of nondestructive SAXS, WAXS, XRD, XPS, EXAFS, and MAS NMR techniques, we were able to verify the phase transformation, shape, size dimension, local bonding, and chemical environments of (CdSe) 13 nanoclusters, which are indicative of a paired cluster model. These experimental results are consistent with the size, shape, bond lengths, dipole moment, and charge densities of the proposed "paired-tubular geometry" predicted by computational approaches. In this article, we revisit the formation pathway of the mysterious (CdSe) 13 nanoclusters and propose a paired cluster structure model for better understanding of II−VI semiconductor nanoclusters.