A common misconception: the Missouri River does not form Missouri's western border. That boundary is the Kansas–Missouri state line, a straight north-south survey line.
The Missouri River flows eastward across the state, entering from Kansas City (where it forms a brief segment of the KS-MO border), then cutting diagonally across central Missouri—through Jefferson City, the capital—before joining the Mississippi River north of St. Louis. It bisects the state, not borders it.
The river's name, its prominence, and its role as the longest U.S. river (3,767 km) lead many to assume it defines the state's edge. In reality, Missouri's western border was established by the 1820 Missouri Compromise and subsequent surveys—a political line, not a natural one.
The river does form parts of other state borders: Nebraska–Iowa, Nebraska–Missouri (briefly), South Dakota–Nebraska, North Dakota–Montana. But in its namesake state, it's a central artery, not a boundary.