A series of bis(pyridyl) acceptor emitters are synthesized and the LC and photophysical (PL and EL) properties of their supramolecular structures, including H-bonded polymer networks and trimers, are explored. Unique mesomorphic properties may be introduced into these H-bonded complexes and polymers containing nonmesogenic acceptor emitters. In addition, the emission properties of bis(pyridyl) acceptor emitters can be adjusted by their surrounding nonphotoluminescent proton donors. Compared with pure bis(pyridyl) acceptor emitters, red-shifts of PL emission wavelengths were observed in most of the H-bonded complexes and polymers. Because of the higher acidity value of m-PC10BA (16) and its stronger H-bonded effect in H-bonded polymer complexes, the largest red-shift of 93 nm in λmax value of PL has occurred in the fully H-bonded polymer network p-PBBBP-OC8 (8)/m-PC10BA (16) in contrast to pure emitter p-PBBBP-OC8 (8). A very narrow full width at half-maximum (fwhm) value (38 nm) of EL spectra can be obtained in the device of H-bonded complexes blended with PVK, and a higher brightness of EL is produced at an appropriate annealing temperature.