Circularly polarized luminescence (CPL) materials have attracted considerable attention for their promising applications in encryption, chiral sensing, and three-dimensional (3D) displays. However, the preparation of high-efficiency, pure blue CPL materials remains challenging. In this study, we reported an enantiomeric pair of triangle copper(I) clusters (R/S-Cu3) rigidified by employing chiral N-heterocyclic carbene (NHC) ligands with two pyridine-functionalized wingtips. These chiral clusters emitted pure blue phosphorescence that overlapped with that of the commercial blue phosphor having Commission Internationale de l'Eclairage (CIE) chromaticity coordinates of (0.14, 0.10), and the films exhibited an unprecedented photoluminescence quantum yield (PLQY) of ∼70.0%. Additionally, the solutions showed very bright circularly polarized phosphorescence (CPP) with a dissymmetry factor of ±2.1 × 10-3. The excellent solubility and photostability endowed these pure-blue-emitting chiral clusters with promising applications as pure blue CPP inks for 3D printing white objects, such as precise-atomic-enlarged models of metal clusters and a lovely white stereoscopic "rabbit". The intricate mechanism underlying blue phosphorescence in this small cluster and across various states is elucidated through a comprehensive approach that integrates thorough analysis of luminescence properties, controlled experiments, and theoretical calculations. For the first time, we propose that the dominant high-energy emission center is constituted by delocalized hybrid orbitals over multiple atomic centers, encompassing both the metal and the coordinated atoms. This challenges stereotypical assumptions that the cluster center solely supports low-energy emissions. This work expands the currently limited range of CPP functional materials and provides a new direction for CPP applications involving NHC-stabilized metal clusters.