Under mild conditions, PPO–PEO–PPO (“reverse Pluronics”) and PBO–PEO–PBO copolyether were generated by way of N-heterocyclic olefin-based organocatalysis. Reverse Pluronics with molar masses > 20 000 g mol⁻¹ could be synthesized with excellent control (Đ_M ≤ 1.03) and were converted into (ordered) mesoporous carbons via organic self-assembly to showcase the need for tailor-made copolymer as structure-directing agent.