The novel phosphinite PPh2(3-OCH2C5H4N) (1) has been synthesized, and its coordination properties to Ag(I) have been studied. When reacted in a 1:1 ratio with Ag(l), coordination polymers with different coordination numbers about the Ag are found depending on the anion. For PPh2(3-OCH2C5H4N)AgBF4 (2), a two-coordinate Ag is observed with a P-Ag-N angle of 167degrees. Mixed three and four coordination about Ag is observed for PPh2(3-OCH2C5H4N)-AgOTf (3), and for the trifluoroacetate derivative, PPh2(3-OCH2C5H4N)Agtfa (4), only a four-coordinate Ag is produced. X-ray crystal-structure determinations for compounds 2-4 have been carried out. The X-ray structures show a wide range of Ag-Ag distances in the polymers, which are dependent on the conformation of the bridging ligand.