Novel supramolecular side-chain banana-shaped liquid crystalline (LC) polymer complexes AmBn-N bearing various (m/n) molar ratios of hydrogen- and covalent-bonded bent-core components were acquired by the free radical polymerization, where the hydrogen-bonded (H-bonded) structures were executed via mixing equimolar portions of proton donor (H-donor) polymers AmBn (homopolymers/ copolymers) and pyridyl proton acceptor (H-acceptor) bent cores (small molecules). The influences of the molar ratios of bent-core H-bonded components in side-chain banana-shaped LC polymers and their corresponding polymer complexes on mesomorphic and electro-optical properties were first investigated, The voltage-dependent antiferroelectric properties of spontaneous polarization (Ps) values in the polar smectic phase of the supramolecular side-chain banana-shaped copolymers were also reported. The nematic and tilted smectic phases were verified by XRD measurements, and the SmCP phase was further confirmed by the triangular wave method. Surprisingly, a novel enantiotropic polar smectic (SmCPA) phase was generated in some bent-core side-chain polymer complexes AmBn-N. Therefore, a special approach to constructing (or stabilizing) the SmCP phase was first developed in this study by copolymerization of bent-core covalent- and H-bonded units in side-chain polymer complexes (with proper m/n molar ratios of 16/1 and 10/1) from both bent-core covalent- and H-bonded monomers (i.e., B and A-N units, respectively) without the SmCP phase.