The Library of Virginia has manuscript records dating from 1801 to 1863 and also cohabitation/marriage records for 1866.

These records are only in Richmond at the library/archives. Below are references taken from: A Guide to Free African American and Slave Records at the Library of Virginian, revised by Research Archivist Derek Gray in June 2005

Original Records:

Box 1 FN&S (4/F/1/5/4)
List of Free Negroes andMulattoes, 1801-1807, 1809, 1811
List of Free Negroes, 1821

Box 1 (Oversized) FN&S (4/F/2/8/1)
List of Free Negroes, 1863

Box 7 FN&S (4/g/1/5/3)
Certificates of Free Negroes, 1855
List of Free Negroes, 1857, 1858, 1860-1862, 1864

Box 94 FN&S (4/f/51/6/7)
Lists of Free Negroes, 1817-1820, 1822, 1823

Barcode 1120490 (no box number) Cohabitation Register (4/f/62/2/1)
Register of Colored Persons Cohabitating Together as Husband and Wife on 27 February 1866

After checking these records, you should also check the court loose papers (I think they're called "Records at Large" in Prince Edward County), common law order books, order books, deeds and wills for references to Free People of Color in the county.

To better understand some of what you're researching, I would recommend that you read the Black Laws of Virginia and the Free Negro in Virginia.

Also in terms of viewing the above recommended court records (everything except the Free Negro registers), you can rent them at your local Mormon, Family History Center.

To see what's available, go to the www.familysearch.org web site and go to the Library section, and search the Library Catalog. Search by location under Prince Edward as part of Virginia. Then select Virginia, Prince Edward - court records. This will show you all that the Mormons have on microfilm.

I hope this helps, happy hunting!