One of what Robert Beverley in 1705 called the "abundance of lesser rivers, many of which are capable of receiving the biggest merchant ships," the Pamunkey River takes its name from the Native American tribe to which Chief Powhatan belonged. The Pamunkey is formed about twenty miles north of Richmond when its two tributary rivers, the North and South Anna, converge. From there the Pamunkey flows (roughly parallel with the James) for about ninety miles, the lower fifty of which are navigable, before joining the Mattaponi to form the York River. The river's basin drains from the Virginia counties of Caroline, Hanover, King William, and New Kent.

The Pamunkey River basin was still uncharted territory as far as Europeans were concerned when German explorer John Lederer in March 1669 made the first of his three trips up the river. He wrote,

I reached the first Spring of Pemaeoncock, having crossed the River four times that day by reason of its many windings; but the water was so shallow, that it hardly wet my horses patterns. Here a little under the surface of the earth, I found flat pieces of petrified matter, of one side solid Stone, but on the other side Isinglas, which I easily peeled off in flakes about four inches square: several of these pieces, with a transparent Stone like Crystal that cut Glass, and a white Marchasite that I purchased of the Indians, I presented to Sir William Berkley Governour of Virginia.

Lederer also noted in detail the wildlife that he encountered—squirrels, wolves, grey foxes, wild cats and "Small Leopards," rattle snakes, bears, beavers, otters, and "Great herds of Red and Farrow Deer." Lederer described the view that opened to him from the Pamunkey's headwaters: "from the top of an eminent hill, I first descried the Apalatean Mountains, bearing due West to the place I stood upon: their distance from me was so great, that I could hardly discern whether they were Mountains or Clouds."

Modern travelers find that much of the Pamunkey remains as Lederer experienced it, for development has been almost nonexistent, tidal marshes and forestation remain intact, and the river is clean. Indeed, many formerly improved lands that included Native American villages and colonial plantations have reverted back to natural habitat. In addition to the wildlife that Lederer described, bird life includes osprey, bald eagles, great blue herons, and a wide variety of waterfowl and songbirds. The river is filled with abundant fish, bluegill, redbreast sunfish, stripers, white and yellow perch, blue and white and channel catfish, small- and largemouth and spotted bass, crappie, carp, long-nose gar, and shad (a shad hatchery is operated by the Pamunkey Indians at the tribe's reservation in King William County). The Pamunkey River's recreational uses include hunting, fishing, camping, canoeing, kayaking, boating, and bird watching.

Perhaps the most famous Pamunkey River settlement was the White House Plantation, the Custis family estate where George Washington and Martha Custis were married in 1760 and which was later owned by Martha's great-granddaughter, Mary Anna Randolph Custis, the wife of Robert E. Lee. During the American Civil War, operations along the Pamunkey were especially important during the Peninsula Campaign of 1862 and the Overland Campaign of 1864. 

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