Medical devices with at least one surface comprising a polymer or polymers on the surface are provided. The polymer or polymers are capable of breaking down (e.g., including, but not limited to, hydrolyzing) in the physiologic milieu to form an active agent or agents under physiologic conditions, and can contain other active agents dispersed within or appended to the polymer matrix. Methods of delivering an active agent to an interior surface of a vein or artery are also provided.