AbstractEmerging technologies for integrated optical circuits demand novel approaches and materials. This includes a search for nanoscale waveguides that should satisfy criteria of high optical density, small cross‐section, technological feasibility and structural perfection. All these criteria are met with self‐assembled gallium phosphide (GaP) epitaxial nanowires. In this work, the effects of the nanowire geometry on their waveguiding properties are studied both experimentally and numerically. Cut‐off wavelength dependence on the nanowire diameter is analyzed to demonstrate the pathways for fabrication of low‐loss and subwavelength cross‐section waveguides for visible and near‐infrared (IR) ranges. Probing the waveguides with a supercontinuum laser unveils the filtering properties of the nanowires due to their resonant action. The nanowires exhibit perfect elasticity allowing fabrication of curved waveguides. It is demonstrated that for the nanowire diameters exceeding the cut‐off value, the bending does not sufficiently reduce the field confinement promoting applicability of the approach for the development of nanoscale waveguides with a preassigned geometry. Optical X‐coupler made of two GaP nanowires allowing for spectral separation of the signal is fabricated. The results of this work open new ways for the utilization of GaP nanowires as elements of advanced photonic logic circuits and nanoscale interferometers.