We have developed a family of novel π-conjugated donor-acceptor-donor (d-a-d) small molecules of amphiphilic nature, aiming to promote intermolecular ordering for enhanced charge separation and transport in organic photovoltaics (OPVs), and charge mobilities in organic thin-film transistors (OFETs). We selected diketopyrrolopyrrole (DPP) as the acceptor moieties that can be di-substituted with non-polar and polar functional groups, thereby providing the amphiphilic nature. Thienylene donor units were chosen due to their relatively low torsional energy barriers to planarity and π-stacking ability. This structural design resulted in materials with strong intermolecular order, which was confirmed by differential scanning calorimetry (DSC), showing two distinct crystallization features above 90 ˚C; the uniaxial alignment of the molecules led to strong birefringence observed via polarized optical microscopy, indicating strong order in the solid state. A high degree of crystallinity in the thin films was seen using grazing incidence wide angle x-ray scattering (GIWAXS). Langmuir-Blodgett (LB) films of well-ordered monolayers at an air-water interface were deposited onto metal oxide substrates; these films, consisting of mono- and multi-layers, were subjected to morphological and transport studies. The crystalline characteristics of these amphiphilic molecules should lead to high charge mobilities, ideal for OFET applications. These materials also exhibit broad absorption spectra extending into the near infrared, high extinction coefficients, and well-aligned energy levels for exciton dissociation at the donor-acceptor interface in OPV devices.