A single atom Ti-Cu(111) surface alloy can be generated by depositing small amounts of Ti onto Cu(111) at slightly elevated surface temperatures (∼500 to 600K). Scanning tunneling microscopy shows that small Ti-rich islands covered by a Cu single layer form preferentially on ascending step edges of Cu(111) during Ti deposition below about 400K but that a Ti-Cu(111) alloy replaces these small islands during deposition between 500 and 600K, producing an alloy in the brims of the steps. Larger partially Cu-covered Ti-containing islands also form on the Cu(111) terraces at temperatures between 300 and 700K. After surface exposure to CO at low temperatures, reflection absorption infrared spectroscopy (RAIRS) reveals distinct C-O stretch bands at 2102 and 2050cm-1 attributed to CO adsorbed on Cu-covered Ti-containing domains vs sites in the Ti-Cu(111) surface alloy. Calculations using density functional theory (DFT) suggest that the lower frequency C-O stretch band originates specifically from CO adsorbed on isolated Ti atoms in the Ti-Cu(111) surface alloy and predicts a higher C-O stretch frequency for CO adsorbed on Cu above subsurface Ti ensembles. DFT further predicts that CO preferentially adsorbs in flat-lying configurations on contiguous Ti surface structures with more than one Ti atom and thus that CO adsorbed on such structures should not be observed with RAIRS. The ability to generate a single atom Ti-Cu(111) alloy will provide future opportunities to investigate the surface chemistry promoted by a representative early transition metal dopant on a Cu(111) host surface.