The first example of heterometallic Ag/Ti bimetallic‐based coordination polymer was synthesized using salicylic acid as the ligand. The uniform Ag/Ti−O rod array has efficient electrocatalytic CO2 reduction activity with a Faradaic efficiency (FE) of 90.3 % at −0.88 V (vs RHE) and a maximum TOF of 658 h−1 at −1.08 V. The chemical catalytic property of the Ag/Ti−O rod was also studied, and the results showed that the Ag/Ti−O rod has good catalytic performance for selective oxidation of sulfide to sulfoxide.