That depends on whether a business or voluntary body has any employed staff. If there are employees, the Health and Safety at Work Act 1974 is applicable and a prosecution for an injured volunteer would be brought under section 3 of the legislation. This is the provision that deals with non-employees such as members of the public, service users and volunteers.
If, however, a voluntary body has no employees, it cannot be prosecuted under the Health and Safety at Work Act because it is criminal law and only applies to employers, employees and the self-employed.
Despite this, under civil law, organisations have a ‘duty of care’ requirement to protect the health, safety and wellbeing of anyone that deals with the organisation; including volunteers, customers, suppliers or even the general public. Reasonable steps should be taken to reduce the probability and seriousness of injuries to volunteers.
Due to the legal duty of care, an injured volunteer can bring a civil claim against an organisation where that duty has been breached. For this and other reasons, it’s generally considered good practice that people working as volunteers are afforded the same level of health and safety protection as employees.
Additional health and safety measures for volunteers may be deemed necessary because they are less familiar with the working environment or have less experience than a regular employee.
See also, Volunteering: How to manage the risks. Guidance for employers from the Health and Safety Executive.