"The Office of the Geographer’s Global Large Scale International Boundary Detailed Polygons file combines two datasets, the Office of the Geographer’s Large Scale International Boundary Lines and NGA shoreline data. The LSIB is believed to be the most accurate worldwide (non- W. Europe) international boundary vector line file available. The lines reflect U.S. government (USG) policy and thus not necessarily de facto control."
http://geonode.state.gov/layers/geonode%3AGlobal_LSIB_Polygons_Detailed#abstract-more
An ongoing project to map all of the world's countries' administrative boundaries, not just country boundaries, but also sub-country (e.g. province or state, county, etc.)