AbstractNonionic double thermoresponsive diblock copolymers with both upper critical solution temperature (UCST) and lower critical solution temperature (LCST) phase transitions are synthesized via eco‐friendly photoiniferter reversible addition–fragmentation chain transfer polymerization. While the biocompatible random copolymer of di(ethylene glycol) methyl ether methacrylate and oligo(ethylene glycol) methacrylate accounts for the LCST transition, the block of polymethacrylamide from an easily accessible monomer with low health hazard is responsible for the UCST transition. Temperature‐dependent dynamic light scattering measurements confirm the formation of micellar aggregates in water at the temperatures below UCST‐ and above LCST‐type cloud points. Additionally, the temperature interval between UCST and LCST, where both blocks are dissolved, can be tailored by varying the comonomer ratio in the random copolymer block. With these unique advantages, the presented work introduces a new polymer system for the design of schizophrenic polymers.