A series of novel rod−rod diblock copolymers containing poly{2,5-bis[(4-methoxyphenyl)oxycarbonyl]styrene} (PMPCS) and poly(γ-benzyl-l-glutamate) (PBLG) were synthesized by click chemistry from alkyne- and azide-functionalized homopolymers. The α-alkyne PMPCS homopolymers were synthesized by copper-mediated atom transfer radical polymerization with a bromine-containing α-alkyne bifunctional initiator, and α-azido PBLG homopolymers were synthesized by ring-opening polymerization of γ-benzyl-l-glutamate N-carboxyanhydride with an amino-containing α-azide initiator. The molecular structures of the rod−rod block copolymers were confirmed by 1H NMR spectroscopy, Fourier transform infrared spectroscopy, and gel permeation chromatography analysis. The self-assembling behavior of the rod−rod block copolymers in bulk was investigated using differential scanning calorimetry, polarized light microscopy, wide-angle X-ray diffraction, and transmission electron microscopy techniques. A lamellar structure was observed w...