Smith will officially step into the role on 27 February next year, with Liebelt retiring from the company on 31 March 2012.
Current CEO Liebelt stated that he "decided it was time to seek a different career challenge after more than 20 years with the Orica Group".
The announcement follows a two year evaluation process.
Smith was previously the CEO at Newcrest for five years, and stood down from the position earlier this year.
His announcement to leave the miner was unexpected and stunned the industry, Smith saying that the time was right, and indicated he would not be looking to become chief executive at another miner.
The Orica board said it was delighted to have secured Smith’s services.
It said it expects him to "drive Orica’s global business into another period of dynamic growth".
Chairman of the board, Peter Duncan, went on to pay tribute to Liebelt’s tenure over the last six years, saying Liebelt has extended the explosives manufacturers’ profile and expanded its position in the mining services industry.