Organometallic palladium adducts have application as catalysts and as precursors for nanoparticle synthesis. Herein, we study the spontaneous formation of molecular crystals of the organometallic reagent tris(dibenzylidenacetone)dipalladium(0) (Pd-2(DBA)(3)) in THF/H2O binary solvent systems. We report structural and chemical characterization of the resulting diverse structures with shapes including hexagonal platelets, rods, cubes, and stars. Optical microscopy, transmission electron microscopy, scanning electron microscopy, and energy-dispersive spectroscopy were used to determine representative structures and corresponding compositions when formed either in a binary,solution or upon evaporation on a Surface. The difference in Pd-2(DBA)(3) particle morphology was attributed to differences in the surface tension of growing crystalline faces. The formation of a majority of rods or hexagonal platelets in solution was shown to be determined by the ratio of THF to H2O in the solvent, whereas supersaturation effects and interfacial surface tension played a major role in creating the shape of particles formed upon evaporation of Pd-2(DBA)(3) droplets on a surface.