Single-crystalline triisopropylsilyl-ethynyl pentacene (TIPS-PEN) micro-ribbons (see figure) with well-defined facets and unprecedented electrical characteristics, such as a field-effect mobility as high as 1.4 cm(2) V-1 s(-1), are fabricated through the self-assembly of individual TIPS-PEN molecules as a result of solvophobic interactions in the solution phase adopting preferential well-ordered intermolecular pi-pi stacking along the ribbon axis.