For next-generation high-capacity, rate-flexible, and secure 400-G passive optical network (PON), a scheme joint wavelength division-multiplexed (WDM), entropy-regulated probabilistic constellation shaping-64-quadrature amplitude modulation (PCS-64-QAM) and chaotic encryption mapping, is proposed and demonstrated. For the first time, chaotic encryption is realized over the PCS-based PON with the architecture from one optical line terminal (OLT) to multiple optical network units (ONUs). Chaotic encryption with an initial-value-sensitive feature can generate a large amount of parallel encrypted sequences which provide a key pair corresponding with every possible entropy/rate. A novel mapping from PCS-64-QAM with various entropies to pseudo- <italic xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">m</i> -QAM is designed, which erases the entropy information of the link and encrypted the original information of the sequence. The encryption transmission is demonstrated over a real-time dual-polarized coherent optical platform with an 80-km link and typically one-to-many PON configuration, and a net 211.80∼348.12-Gb/s rate result within the hard-decision forward error correction (FEC) threshold is achieved for 6λ × 2 ONUs group. The rate of each polarization state can be tuned in a minimum 3.408-Gbps step in the demonstration. Expanding from the basis of the original WDM-CPON, this work prepares an adapted chaotic encryption scheme for large-scale access. Overall, our proposed scheme can provide an abundant system loss budget, a large rate tunable range, and basic physical layer security for next-generation rate-flexible coherent PON (FLCS-CPON).