Edwards already has an outstanding pedigree as a head coach after leading Ebbw Vale to two successive WRU Division One titles and creating the backbone of the Steelmen side that won this year's Championship.
The Llwynpia-born 36-year old turned out for Newport Gwent Dragons and Wales A in a long and successive playing career.
He also had seasons with Ebbw Vale, Newport and Neath, where he helped the Blacks to win two successive league titles.
Edwards is delighted to be coach of Wales' most famous club side and he is hoping to restore them to former glories.
"We have a big task in front of us," he said. "I'm looking forward to rolling my sleeves up and getting into it.
"We need to get some stability into the side this season. We've signed a lot of the current group for next season already and we'll also be strengthening.
"We know it's essential to have a good build up. We've a 12-week pre-season to prepare for a successful Neath campaign for 2013-14."
Edwards paid respect to departing coach Pat Horgan who has both played and coached alongside.
"I've known Pat for a long time and I was disappointed to see him go," Edwards said. "I wish him all the best for the future."
Neath chairman Phil Davies said: "We're delighted that Neil has accepted the position of head coach. He has a fantastic record both as a player and head coach already and we're certain he'll do an excellent job for the club.
"Neil is now assembling his back-room staff and building a squad for the new season.
"There will be a number of new faces involved and all concerned are under no illusion of what's required to put our proud and mighty club back on the summit of Welsh Premiership rugby."