2D microstructures of N,N'-diphenyl-N,N'-bis(1-naphthyl)-1,1'-biphenyl-4,4'-di-amine (NPB) have been prepared by a facile solution method and fully characterized. The as-prepared NPB microsheets have well-defined shapes and very smooth surfaces, and are ideal building blocks for 2D optical waveguides. The results indicate that the optic losses within NPB microsheets are closely related to the direction of propagation, and the shape of microsheets can change the direction of waveguiding light. Such 2D optical waveguides may have potential applications in future miniaturized light-based circuits serve as interconnectors different from 1 D optical waveguides.