Suppression of self-quenching of fluorescence emission in supramolecular systems is of fundamental interest in the design and development of novel optical materials. While a number of molecular design and assembly strategies have been formulated for the fabrication of molecular crystals with enhanced light emission, parallel explorations based on systematic approaches in the domain of molecular ultrathin films are rare. We have investigated Langmuir-Blodgett films of amphiphilic molecules bearing the same hemicyanine choromophore headgroup but with different possibilities of attachment of the octadecyl hydrocarbon chain, under different deposition conditions. Fluorescence spectroscopy studies indicate enhanced light emission in the derivative with a "tail-head-tail" structure. The observed trends are attributed to the amphiphile structure, nature of deposition, and the chromophore orientations revealed through polarized absorption spectra of the films. The study suggests a simple design strategy toward realization of molecular ultrathin films with enhanced light emission.