Eight pioneer families settled in Alfred. The following is a list of the heads of these families:
- Allen, Abram
- Allen, George W. (Deacon)
- Allen, John
- Allen, Joshua
- Babcock, Daniel (Elder)
- Benjamin, Silas
- Benjamin, Thomas
- Burdick, Abel
- Burdick, Amos, Sr.
- Burdick, Amos, Jr. (Deacon)
- Burdick, Asa
- Burdick, Elias G.
- Burdick,Enos P.
- Burdick, Isaac, Sr.
- Burdick, Isaac, Jr.
- Burdick, Ethan C.
- Burdick, James
- Burdick, Jeremiah
- Burdick, Thomas T.
- Burdick, William D.
- Champlin, Bradford
- Champlin, George W. (Deacon)
- Collins, John Bowen (Dr.)
- Collins, Stephen
- Coon, Elisha
- Coon, Jared
- Coon, Stephen
- Crandall, Amos (Deacon)
- Crandall, Clark (Judge)
- Crandall, Henry Beebe
- Crandall, Silas
- Edwards, Joseph
- Fenner, Isaac
- Fisk, James C.
- Greene, Benjamin
- Greene, Edward (Judge)
- Greene, Edward, Jr
- Greene, Edward,Sr
- Greene, George
- Greene, Joseph
- Greene, Luke (Sugar Hill)
- Greene, Luke (Merchant)
- Greene, Nathan
- Greene, Paris
- Greene, Ray (Elder)
- Hamilton, Freeborn
- Hull, Richard (Elder)
- Lanphear, Maxson
- Lanphear, Samuel
- Lewis, Elijah
- Maxson, Benjamin
- Maxson, Luke, Jr.
- Palmiter, Jonathon, Sr.
- Palmiter, Jonathon, Jr.
- Place, Rodman
- Potter, Edward
- Potter, Elisha
- Potter, Nathan (Colonel)
- Potter, Perry
- Saunders, Christopher
- Saunders, Ezekiel R.
- Saunders, George
- Saunders, William
- Satterlee, David (Deacon)
- Sheldon, Henry Beebe
- Sherman, George
- Sherman, Josiah
- Smith, Ashbel
- Smith, Elias, Sr.
- Smith, Elias, Jr.
- Stillman, David
- Stillman George (Deacon)
- Stillman, Maxson, Sr.
- Stillman, Maxson, Jr.
- Stillman, Silas, Sr.
- Sweet, Spencer
- Thomas, Rowland P.
- Vincent, Joshua, Jr.
- Whitford, Jesse
- Williams, Nathan C.
- Witter, Clark
- Witter, Paul
- Woodworth, Elijah