The new mentors, who can be accessed through mentorsme.co.uk, are now available in addition to 12,000 existing mentors from other organisations.
The volunteer mentors were recruited through the £1.9 million government-funded Get Mentoring service, delivered by the Small Firms Enterprise Development Initiative (SFEDI).
The aim of the mentorship scheme is to provide experience and advice to those starting out in business across the country.
Business minister Michael Fallon said: “We have invested in mentoring because we know that good mentors can provide the practical advice and support that an entrepreneur needs to take their business idea to the next level. They have been there and done it and can pass that experience on. I want to encourage people to come forward and take advantage of the mentoring network.”