Responding to a poll that found a majority of doctors believe having more GPs in emergency departments could ease pressure on hospitals, the college warned that the move risked having the 'opposite effect'.
Hospitals are struggling to hit key performance targets, with performance against the four-hour A&E waiting time target at its lowest level for more than a decade.
The college's comments came in response to a Press Association survey of 500 doctors, which found that 61% believed GP surgeries should be introduced in A&E departments.
RCGP chair Professor Helen Stokes-Lampard said: 'We are keen to see GPs and hospitals working closely together in the best interests of patients and there are some parts of the country where schemes like this are already working very successfully.
'But the best place for GPs is in their surgeries caring for their patients close to their homes in their own communities.
'There is also the risk that any expansion of programmes using GPs at the front end of hospitals might have the opposite effect to what is intended and encourage patients to use emergency departments as a first port of call for minor illnesses.'
She warned that GPs were 'already working flat out and preventing thousands of inappropriate hospital admissions every day'.
The real solution to easing pressure on hospitals, the RCGP warned, was to increase GP funding to allow more patients to be treated closer to home.