Perylene diimides (PDIs) represent a relatively rare class of n-type organic semi-conductors that show promise for uses in OLEDs, solar energy conversion and many other applications where electron transport in organic media is required. In this work it is shown that by sequential deposition of novel asymmetric, water soluble perylene diimides and polyelectrolytes onto a clean glass coverslip a nanofibrous film if formed. The dipping cycle consists of exposure of a clean glass slide to an aqueous solution of PDI, followed by a rinse in water, then exposure to a solution of polyelectrolyte, followed by another rinse step. This procedure is repeated as necessary to obtain a film of desired thickness. By using this sequential deposition process the films are effectively being “solvent annealed”, thus forming structures that have more order than films prepared by other deposition methods. Absorption studies of these films show a linear increase in absorbance with the number of deposition cycles. Tapping mode atomic force microscopy reveals the fibers have lengths of tens of microns and widths that depend on the number of deposition cycles. Polarized fluorescence microscopy shows chromophore alignment to be perpendicular to the fiber longitudinal axis. With this information and consideration of intermolecular interactions (pi-pi interactions, electrostatic interaction, and hydrophobic/hydrophilic interactions) a model of perylene-polyelectrolyte binding is presented.