On-surface synthesis has been a subject of intensive research during the last decade. Various chemical reactions have been developed on surfaces to prepare compounds and carbon nanostructures, most of which are centered on the carbon–carbon bond formation. Despite the vast progress so far, the diversity of functional groups in organic chemistry has been far less explored in on-surface synthesis. Herein, we study the surface-assisted synthesis of ethers through the homocoupling of hydroxymethyl substituents on Ag(111). By using two hydroxymethyl substituent functionalized molecular precursors with different symmetries, we have achieved the formation of ether chains and rings. High-resolution scanning tunneling microscopy complemented with density functional theory calculations are used to support our findings and offer mechanistic insights into the reaction. This work expands the toolbox of on-surface reactions for the bottom-up fabrication of more sophisticated functional nanostructures.