This article is concerned with the study of conformal growth of thin gallium phosphide (GaP) layers by plasma-enhanced atomic layer deposition (PE-ALD) on a Si structured surface. GaP layers were deposited on (100) silicon wafers with a structured surface in the form of silicon microcolumns and black silicon. Deposition process were carried out at temperature of 380 °C using trimethylgallium and phosphine precursors. According to transmission electron microscopy (TEM), GaP layers deposited by this method conformally grown on the high aspect ratio structured silicon surface. The energy-dispersive X-ray spectroscopy (EDX) study show that the distribution of the main components of the GaP layer is uniform alongside surface of the silicon microcolumns and wires. High resolution TEM study confirms that GaP layers on the surface of silicon microcolumns and wires are epitaxial with the inclusion of twin lattice defects. Therefore, this deposition method can be used for the conformal deposition of thin crystalline layers of GaP on structured silicon surfaces with a high aspect ratio.