It said in a statement that, in terms of the transaction, it had agreed to acquire the assets (excluding foreign entities) and to assume certain liabilities of CNA, valued at R11m, for a net purchase price of approximately R130m.
The transaction is subject to the approval of relevant court and competition authorities.
Edcon will be taking over approximately 137 CNA stores, dependent on the cession of leases by the landlords.
"This is a very positive transaction for Edcon," Edcon chief executive Steve Ross said.
"We will be able to expand our retail offering profitably through product lines that are complementary to those currently offered across the group. We have a very similar customer base as the majority of the CNA stores are in the same cities or trading nodes as Edcon stores."
Edcon, the clothing group which owns Edgars, Jet, Sales House and Cuthberts chains, expects CNA's turnover in the first full trading year to be approximately R800m.
CNA is a retailer of books, stationery, magazines, music, interactive computer software and toys.