The officers fell ill after they forced entry to a property at Park Hill flats, off Duke Street, on Monday evening following a report that a man had been found with injuries outside the building.
The man, aged in his 30s, was given CPR at the scene and was taken to hospital, where he remains in a serious condition, South Yorkshire Police said.
A force spokesman said there are no suspicious circumstances surrounding how the man was injured and the property is now free from contamination.
He said: “At 6.04pm, we received a report from a member of the public that a man had been found with injuries outside the flats.
“This led to concerns about the flat the man lived in, so officers forced entry to assess the property.
“There, they came into contact with a chemical substance, now believed to be a number of household products, and four officers needed minor medical attention and support.”
The officers attended Northern General Hospital for further tests and were all discharged with no further symptoms or complications.
Police said officers would be available to talk to residents but said there are no concerns for their safety or that of the wider public.