Here is an earlier article for the product details of the blu-ray set and US pre-order link.
Episodes from the set are introduced by Rod Roddenberry, son of Star Trek creator Gene Roddenberry.
Episodes include: The Cage, Where No Man Has Gone Before, Space Seed, Errand of Mercy and Trouble with Tribbles.
Released on 2nd September, 2013. Pre-order now from Amazon UK for £8.14