Abstract Achieving white‐light emission, especially white circularly polarized luminescence (CPL) from a single‐phase material is challenging. Herein, a pair of chiral Cu I coordination polymers ( 1‐M and 1‐P ) have been prepared by the asymmetrical assembly of achiral ligands and Cu 2 I 2 clusters. The compounds display dual emission bands and can be used as single‐phase white‐light phosphors, achieving a “warm”‐white‐light‐emitting diode with an ultra‐high color rendering index (CRI) of 93.4 and an appropriate correlated color temperature (CCT) of 3632 K. Meanwhile, corresponding CPL signals with maximum dissymmetry factor | g lum |=8×10 −3 have been observed. Hence, intrinsic white‐light emission and CPL have been realized simultaneously in coordination polymers for the first time. This work gains insight into the nature of chiral assembly from achiral units and offers a prospect for the development of single‐phase white‐CPL materials.