Polymerization‐induced self‐assembly (PISA) has emerged as a scalable one‐pot technique to prepare block copolymer nanoparticles. Recently, we developed a PISA process that resulted in poly(L‐lactide)‐b‐poly(ethylene glycol) block copolymer nanoparticles coined ring‐opening polymerization‐induced crystallization‐driven self‐assembly (ROPI‐CDSA). The resulting nanorods demonstrated a strong propensity for aggregation, resulting in the formation of 2D sheets and 3D networks. Here, we report the synthesis of poly(N,N‐dimethyl acrylamide)‐b‐poly(L)‐lactide block copolymer nanoparticles by ROPI‐CDSA utilizing a two‐step, one‐pot approach. A dual‐functionalized photoiniferter was first used for controlled radical polymerization of the acrylamido‐based monomer, and the resulting polymer served as a macroinitiator for organocatalyzed ring‐opening polymerization to form the solvophobic polyester block. The resulting nanorods are highly stable and display anisotropy at higher molecular weights (>12k Da) and concentrations (>20% solids) than our previous report. This development expands the chemical scope of ROPI‐CDSA block copolymers and provides readily accessible nanorods made with biocompatible materials.This article is protected by copyright. All rights reserved