A solution of poly(4-vinyl-pyridine) in pyridine is converted into a gel over a 3 week period. The spontaneous self-organization is governed by interchain hydrogen bonding. These interactions resulted in a change of polymer's optical properties. Blue, green, and red emissions appear in the gel by appropriate excitation wavelength replacing the initial dark blue emission. Energy transfer between emitting centers is restricted because of the insulating nature of the polymer backbone.