We report an on-surface synthesis of five-membered carbon ring via a [4 + 1] annulation reaction, starting from a simple terminal alkynyl bromide, 4-(bromoethynyl)biphenyl, on Ag(110). The combination of scanning tunneling microscopy (STM), synchrotron radiation photoemission spectroscopy (SRPES), and density functional theory (DFT) calculations unravel the reaction pathway and mechanism. Three basic reaction steps are involved, successively including the formation of alkynyl-Ag-alkynyl bridged organometallic dimer, the generation of alkylidene carbene intermediate, and the final [4 + 1] annulation involving a hydrogen transfer step.