Original proprietors of the town were some of the first to inhabit the region, namely, Thomas Whitmore and sons in the Attawaugan area, John Allyn and son, Jabez, in the vicinity of Route 21 and Putnam-Killingly town line, Matthew Allyn, son of John, in the Pineville or Ballouville region, Ebenezer MacKee near Pineville, southeast of the meetinghouse, and William Moffitt and sons to the southwest of Allyn.

Other early settlers include Daniel Lawrence, who purchased MacKee's property in the early 1720's, and David Russell and family.  Neil Ellick-Saunders (Alexander) purchased land around the lake which now bears his name in the early 1720's and soon also had extensive holdings in the Attawaugan area and around the Five Mile River.  The Chestnut Hill purchase extended to Horse Hill (Yosemite Valley Road), so some of these settlers also owned property within the region.

As early as 1725, a grist mill was located on the Five Mile River, apparently a little north of the present Daniel's Village site.  Operated at first by men from Chestnut Hill, it changed ownership many times during the early 1700's.

The first resident of the Pineville area was evidently Enoch Moffitt, son of proprietor William Moffitt who had moved to Thompson parish.  In the late 1730's and early 40's, the Rev. Fiske sold several hundred acres around Five Mile River.  Moffitt was one of the purchasers; Gideon Draper was another.

The Rev. Fiske, himself, never lived in the area despite its proximity to the meetinghouse, residing instead in the triangular area across from the Putnam Heights Cemetery.

From the Windham County Transcript, March 3, 1904

The Danielsonville Cotton Co. has recently installed five drop box looms and have commenced the manufacture of colored bordered handkerchiefs. The colors are woven in, not stamped, and when finished make very attractive goods.  This is a new industry here and a very remunerative one to the weavers.  It is expected to gradually develop this branch of the business so that more looms may be added.