Organic semiconducting crystals are characterized by anisotropic optical and electronic properties, which can be tailored by controlling the packing of the constituent molecules in the crystal unit cell. Here, the synthesis, structural characterization, and emission of anthracene derivatives are focused to correlate directed functionalization and optical properties. These compounds are easily and scalably prepared by standard synthesis techniques, and alterations in functional groups yield materials with either exclusive edge-to-face or face-to-face solid-state interactions. The resulting crystals feature either platelet or needle shapes, and the emission exhibits polarization ratios up to 5 at room temperature. In needle-shaped crystals, self-waveguiding of the emission is also observed with propagation loss coefficients as low as 1.3 dB mm. Moreover, optical coupling between crossing crystalline microwires is found and characterized. The combination of optical anisotropy and emission self-waveguiding opens interesting routes for the exploitation of these active materials in photonic applications, including optical integrated circuits and microscale light sources.