"As a former teacher myself, I couldn't put hand on heart and say I've ever told a pupil, 'you're very good, you should think of starting your own business'," Mrs Orr said.
"We might have said, 'you should become a chef or get a job in the tourist industry or think of going to the textile factory up the road'. We are very good too at spotting and supporting pupils' academic potential - but never their business prospects."
Mrs Orr also urged enterprise programmes to aim at all departments, not just those offering vocational subjects.
"I would like to see it more firmly embedded in the curriculum and in other ways. In the Royal High in Edinburgh, for example, the head there wants all his teachers to be trained in enterprise because he wants them to be enterprising teachers."
The Get Into Enterprise initiative for secondary schools, for which Mrs Orr is responsible, now has 3,000 registered tutors and 21,000 students have gone through the programme.