A2BA2-type amphiphilic liquid crystalline block copolymers containing azobenzene were synthesized by atom transfer radical polymerization (ATRP). The macroinitiator prepared by the esterification reaction between poly(ethylene glycol) (PEG) and 2,2-dichloroacetyl chloride was used to initiate the ATRP of 6-[4-(4-ethoxyphenylazo)phenoxy]hexyl methacrylate (M6C). The resulting macroinitiator and block copolymers were characterized by 1H NMR, gel permeation chromatography (GPC). Polarizing optical microscopy (POM) and differential scanning calorimetry (DSC) preliminarily revealed the liquid crystalline property of these block copolymers. These novel amphiphilic liquid crystalline block copolymers are promising in some areas, such as optical data storage, optical switch, and molecular devices.