A one-dimensional asymmetric photonic crystal with dual-frequency liquid crystal as a central defect layer was demonstrated. Such asymmetric structure was characterized by the dramatic increase in intensity of the electric field of light localized at the overlapped photonic bandgap edges, thereby enhancing the observed transmittance of the spectral windows originating from the defect layer. The defect layer was made of a dual-mode liquid crystal that exhibited not only electrical tunability and switchability but also optical bistability. Consequently, tunable and bistable defect modes can be realized in the photonic structure. This asymmetric photonic crystal structure is promising and should be further explored for photonic device applications.