A series of side-chain supramolecular polymer complexes containing proton acceptor triblock copolymer, i.e., poly(4-vinylpyridine)-block-polystyrene-block-poly(4-vinylpyridine) (VSV, i.e., P4VP-PS-P4VP), hydrogen-bonded (H-bonded) with two generations of proton donor bent-core mesogenic dendritic pendants (G1 and G2) were prepared and investigated. These two supramolecular polymer complexes (i.e., VSV/G1 and VSV/G2) were characterized by wide- and small-angle X-ray scattering (WAXS and SAXS), and the formation of a microphase separated smectic A (SmA) structure corresponding to a head-to-head layered arrangement was confirmed. The hierarchical structures within the morphologies of supramolecular polymer complexes were proved not only by the SAXS patterns but also by the transmission electron microscopy (TEM). The novel hierarchical lamellar domains of corresponding tetragonal and hexagonal arrangements in different generations of dendritic proton donors (G1 and G2) were self-assembled with triblock copolymer proton acceptor VSV to induce respective BCC (body-centered cubic) and FCC (face-centered cubic) structures in supramolecular polymer complexes VSV/G1 and VSV/G2. Therefore, the shear alignments of characteristic cylindrical column phase micro-domains were developed for the first time to control the unique hierarchical constructions of functionalized self-assembled bent-core structures by utilization of various generations of dendritic proton donors to be H-bonded with triblock copolymer proton acceptor.