The former Netherlands and Korea Republic coach will be allowed by his club to combine the two roles until Australia complete their qualifying programme in November.
If he manages to steer Australia to the FIFA World Cup he will then coach them until the end of the competition and possibly beyond.
"If the final details are filled in I will have two jobs until November Hiddink said.
Hiddink has flown from a pre-season training camp in Korea Republic to Australia to iron out the details of the agreement.
He guided the South Korean co-hosts to the semi-finals in 2002 after coaching the Netherlands at France '98.
"The two jobs until November are a fact Hiddink added.
"The presentation in Australia will probably take place on Friday. But I will stay on at PSV. At first I will be no more than an adviser (with Australia)."
Australia's former coach Frank Farina stepped down last month after six years in charge. "