Abstract: | Organic micro‐heterostructures (MHS) with dual optical emissions are essential to produce miniaturized optical waveguides for wavelength division multiplexing technologies. The bimolecular MHS produced by solution‐based bottom‐up self‐assembly technique often leads to poor surface smoothness, edge imperfection, defects, and unwanted thin films deposits. Conversely, sequential sublimation technique at ambient pressure facilitates effective integration of α‐perylene micro‐square with dicyanomethylene‐2‐methyl‐6‐(p‐dimethylaminostyryl) 4H‐pyran (DCM) microrods in an epitaxial manner to produce MHS. The obtained DCM/perylene MHS act as optical waveguides to produce red (λmax≈670 nm) or/and yellow (λmax≈607 nm) dual optical outputs via an energy transfer mechanism depending upon the heterostructures geometry and optical excitation positions. The presented dual‐color emitting MHS optical waveguides are essential for the integrated nano‐photonic and optoelectronic device structures. |