The Mid North Coast is expected to hit 39 degrees, while the North West Slopes will crack 40 degrees.
The Northern Rivers, South Coast and Plains districts can expect temperatures up to 37 degrees.
All areas may experience thunderstorms following the heat.
Meanwhile, parts of Sydney are expected to reach 37 degrees, including Cronulla, Penrith, Parramatta, Blacktown, Canterbury and Sydney Olympic Park.
The heatwave is expected to continue through the weekend, with total fire bans in place in the Illawarra, Sydney, Hunter Northern Slopes, North Western and Central ranges area.
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Bushfire Danger Ratings are also at emergency levels, with 61 bushfires burning at advice level across the state by 6.30am.
Hottest month in human history recorded
Humidity levels were as high as 98 per cent in Grafton, NSW this morning, while Sydney hit 99 per cent humidity in Richmond by 6.30am.
Residents have been warned to stay hydrated and remain in shaded areas.
Temperatures won’t be as severe as last week when Saturday got as hot as 43.5 degrees in Sydney’s west