We report the synthesis and spectroscopic study of a new molecularly engineered multilayer structure. The chromophore, which is an oligomer of poly(p-phenylenevinylene), is analogous to polymeric PPV which has been used in the fabrication of LEDs. This study was initiated specifically to explore if a multilayer geometry would aid the transport properties of the material leading to better semiconductor performance. We describe the synthesis and film formation of these novel materials. Detailed dynamic photophysical measurements on several new multilayer materials have shown that spectroscopically these thin films behave similarly to the polymers. The quantum yields of the films are of the same order of magnitude indicating that the emissive properties in both materials are due to localized molecular interactions. The relevance of the material properties to device applications is discussed.