Uniform silicon nanowires (SiNW) were successfully fabricated on the top, bottom, and sidewall surfaces of silicon microchannels by using a two-step electroless etching process. Different microchannel patterns with the channel width from 100 to 300 μm were first fabricated in a 10 mm × 10 mm silicon chip and then covered by SiNW with an average height of 10–20 μm. The effects of the microchannel geometry, micro/nano-hierarchical structures on pool boiling were studied and the bubble dynamics on different sample surfaces were compared. It was found that the combination of the micro/nanostructures promoted microbubble emission boiling under moderate heat fluxes, and yielded superior boiling heat transfer performance. At given wall superheats, the maximum heat flux of the microchannel with SiNW was improved by 120% over the microchannel-only surface, and more than 400% over a plain silicon surface. These results provide a new insight into the boiling mechanism for micro/nano-hierarchical structures and demonstrate their potential in improving pool boiling performance for microchannels.