A precursor polymer PEO‐b‐PEMA that contains anilino moieties is synthesized from EPAEMA by ATRP by using a PEOBr macroinitiator and CuBr/HMTETA catalyst system. The aminoazobenzene‐containing block copolymer PEO‐b‐PCN is obtained by the azo‐coupling reaction between PEO‐b‐PEMA and the diazonium salt of 4‐aminobenzonitrile. Results show that PEO‐b‐PCN has a narrow molecular weight distribution and the repeat unit numbers of the hydrophilic and hydrophobic blocks are 122 and 200, respectively. PEO‐b‐PCN can form uniform spherical aggregates by gradually adding water into its THF solution. Upon irradiation with a linearly polarized Ar+ laser beam, the spherical aggregates can be significantly elongated in the polarization direction of the light.
