The town was named for Samuel Livermore, a former United States senator who was the grandfather of Daniel Saunders' wife.

[3] To the south is Waterville Valley, to the north and west is Lincoln (and a southern tip of Bethlehem), and to the east are Hart's Location, Bartlett and the northwestern corner of Albany.

The village of Livermore was benchmarked with an elevation of 1,264 feet (385 m), a quarter mile from the eastern boundary adjoining Hart's Location.

The original boundary between the two towns did not follow natural features, such as the crest of the divide that separates the Pemigewasset River and Saco River drainages, which led to numerous charges and countercharges of cutting over the line between the two owners, the Saunders family in Livermore and James Everell Henry in Lincoln.

This definition produced a peculiar result: there is a small piece of Livermore at the head of the Little River valley (part of the Ammonoosuc River drainage) that is not contiguous to the rest of the town - it is, in fact, 4.8 miles (7.7 km) from the nearest corner of the main part of the town and, therefore, forms an exclave.

Since this fragment and all lands bordering it are now part of the White Mountain National Forest, this historical peculiarity no longer has any practical consequences.