A polymeric film of a biodegradable poly(1,5-dioxepan-2-one) (PDXO) was formed on a gold surface by a combination of the formation of self-assembled monolayers (SAMs) presenting hydroxyl groups and the surface-initiated, ring-opening polymerization (SI-ROP) of 1,5-dioxepan-2-one (DXO). The SI-ROP of DXO was achieved by heating a mixture of $Sn(Oct)_2$, DXO, and the SAM-coated substrate in anhydrous toluene at $55^{circ}C$. The resulting PDXO film was quite uniform. The PDXO film was characterized by polarized infrared external reflectance spectroscopy, X-ray photoelectron spectroscopy, time-of-flight secondary ion mass spectrometry, atomic force microscopy, ellipsometry, and contact angle goniometry.