The rod-like assembly from BAB block copolymer with hydrophilic middle block A in aqueous solution was described. The copolymer used is polystyrene (PS)39-b-poly(4-vinylpyridine)(P4VP)98-b-PS39 (the subscripts are the average polymerization degree of corresponding blocks) triblock copolymer with Mw/Mn = 1.15. The aggregates were characterized by transmission electron microscopy and atomic force microscopy. The dependence of rod-like aggregate formation on solvents, pH, and polymer concentrations was investigated. The rod-like aggregates were formed when using dioxane as initial solvent, while spherical micelles were formed using DMF. Elevating pH values from 4 to 5 to 7 and decreasing initial copolymer concentrations from 1.5 wt% to 1.0 wt% to 0.5 wt% were favorable for the formation of well-defined rod-like aggregates. In addition, the bicontinuous rods and lamellae were observed when preparing colloid solutions in appropriate conditions.