Novel azobenzene‐containing block copolymers (BCs) with a polyester block bearing azobenzene moieties in the side chain and a poly (methyl methacrylate) (PMMA) block have been synthesized by the combination of atom transfer radical polymerization (ATRP), polycondensation, and “click” chemistry. Two azide‐terminated polyesters with different molecular weight (obtained by polycondensation) were coupled to an alkyne‐functionalized PMMA (obtained by ATRP). Blends of the BC with the highest azo content (wt%) and an azopolyester homopolymer were also prepared. All these compounds were investigated by polarized light optical microscopy (POM), differential scanning calorimetry (DSC), and transmission electron microscopy (TEM). Polarized light‐induced anisotropy was studied by birefringence and dichroism measurements.