The 43-year-old, whose coaching career has also included a spell with Orange Free State in South Africa, made his name as a player when he scored over 15,000 first-class runs in 13 seasons for Warwickshire and Orange Free State.
He was also a member of the highly successful Warwickshire teams in the mid-90s. He scored over 4,500 runs in first class one day games.
The appointment of Moles comes at the start of Scotlands most important season for many years, centred round the ICC Trophy which takes place in July in Ireland, where five places are at stake for the World Cup in the West Indies in 2007.
There are also 18 games in the English one-day league and a match against Australia, the world champions, in August.
"I saw the squad when they played against Kenya in the InterContinental Cup in Dubai last November. They looked a well-organised and dedicated bunch, and Im delighted to have the chance to work with them," said Moles.
"Im also looking forward to the challenge. The target, quite simply, is to qualify for the World Cup."