Two-thirds of the employees polled said schools, colleges and universities could have done more to prepare them for work.
And close to half (45 per cent) said their education did not help them cope with their first job.
The findings will re-ignite the debate over whether schools are doing enough to prepare young people for work.
But they appear to contradict complaints from the Confederation of British Industry that too many school-leavers lack basic skills in English and maths.
Four out of five respondents said schools and colleges had done more than employers to develop literacy and numeracy.
The poll found those who left education in their teens were more negative about it than those who stayed on into their twenties.
Ofsted warned that many 16 and 17-year-olds start work with little confidence.
The 544 employees aged 20-30 surveyed said employers were better than teachers and lecturers at developing key skills.
Employers were rated best in developing eight out of 13 skills: developing teamwork; interview skills; problem-solving; accuracy and attention to detail; meeting deadlines; ability to work alone; and verbal communication.
By contrast, schools and colleges had a clear lead only in numeracy, written communication, presentational skills and information and communications technology.
Schools also led on creativity but answering separate questions, twenty-somethings complained their education failed to encourage them to take risks, challenge ideas or be creative.
However, they did not think teachers and lecturers should shoulder the whole burden of preparing people for working life.
One in nine people - rising to almost a fifth of those working in small companies - complained their employers were not helping to fill gaps in their skills.
Robert Green, Ofsted director of corporate services, called for employers and schools to work together to ensure young people get the skills they need.
He said: "Businesses need employees with a 'can-do' attitude, a willingness to take on responsibility, a creative and innovative approach to solving problems and the ability to cope with uncertainty. The question is how do we ensure young people develop these skills?
"It's no secret that employers and educationists have had, at best, a piecemeal relationship in the past. Current government thinking aims to rectify this."