RCGP chair Professor Martin Marshall has written to health and social care secretary Matt Hancock to demand clear guidance that will reassure GPs and practice staff.
The college said GPs are reporting concerns over the quality of PPE they are being asked to use - with GPs particularly concerned about the standard of aprons they are being asked to use and a lack of eye protection.
Professor Marshall wrote: 'GPs across the country have never been more concerned, not just for the safety of themselves and their teams, but for patients too.
'Our members are telling us that their confidence to carry out patient consultations is being impacted by uncertainty over the quality of PPE being supplied to their surgeries.
'This is particularly relevant for aprons and eye protection, which many believe to be providing inadequate protection. We note that the WHO recommends that GPs should be using eye protection for consultations, yet most practices do not yet have sufficient access to it and there are outstanding concerns around the use of aprons and whether clinicians should have full body cover when seeing patients.'
The letter comes just 24 hours after GPonline exclusively revealed that more than four in five GPs are not satisfied with the quality or quantity of PPE supplied to their practice.
The BMA, meanwhile, has warned that doctors will die without adequate PPE during the COVID-19 outbreak. A total of 9,529 cases have now been confirmed in the UK, with 463 deaths.
BMA deputy chair Dr David Wrigley told GPonline on 25 March that GPs are now seeing only patients who are very ill face-to-face - and should be wearing PPE in all of these consultations.
Professor Marshall warns in his letter to the health and social care secretary: 'As the situation develops further, GPs will see an increasing number of patients with COVID-19. While many of these patients will have symptoms associated with the virus, there are those who will present asymptomatically, particularly in primary care settings, but could still be infectious. It is therefore vital that urgent clarity is provided as to whether GPs should begin wearing PPE for all face-to-face patient consultations.'
The RCGP chair also highlighted concerns over supplies of PPE - with reports that some practices have been told to buy their own and have resorted to trying to purchase kit from DIY stores.
GPonline reported this week that innovative GPs in Surrey have begun 3D printing face visors to reassure staff during face-to-face consultations with patients.
A DHSC spokesperson said: 'We are working around the clock to give the social care sector and wider-NHS the equipment and support they need to tackle this outbreak.
'We have delivered millions more items of personal protective equipment (PPE) for frontline staff at care homes, home care providers and hospices as well as to hospitals, ambulance trusts, GP practices and pharmacists.
'The full weight of the government is behind this effort and we are working closely with industry, social care providers, the NHS, and the army to ensure the right equipment continues to be delivered.'