The charter sets out a series of guidelines to be followed by charities and other employers that work with volunteers. The principles include making sure volunteers receive "reasonable out-of-pocket expenses" and have access, alongside paid workers, to training and development.
Volunteering England hopes the charter will be signed by charities, businesses and other volunteer-involving organisations, such as community groups.
The charter also states that "the involvement of volunteers should complement and supplement the work of paid staff, and should not be used to displace paid staff".
The TUC has also produced guidance to accompany the charter. It says that "while volunteers are not entitled to the same rights as an employee, such as the minimum wage, holiday and sickness pay, they should still receive some form of agreement from the organisation they are volunteering with".
It adds that such agreements should include information about the type of work the volunteer will be doing and the support they can expect from the organisation.
Brendan Barber, general secretary of the TUC, said: "An increasing number of interns and volunteers have been taken on during the recession. With so many people concerned about their jobs, it's vital that employers make a clear distinction between volunteers and paid staff."
The charter says there are 22 million volunteers in the UK and their contribution to the economy and society is worth £23bn a year.