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The Bureau of Meteorology (BoM) said damaging winds and large hail could hit the Blue Mountains, Hunter region and Illawarra this afternoon.
“A trough moving north along the coast is leading to thunderstorm development on the ranges inland from the coast,” the BoM said in a statement.
The BoM warned severe thunderstorms were detected on the weather radar near Penrith, Branxton and Bargo at about 3.45pm.
The storms are expected to affect Springwood, Richmond and Windsor by 4.15pm and Colo, Maroota and Wisemans Ferry by 4.45pm.
Locations that may be affected include Gosford, Cessnock, Maitland, Penrith, Bowral and Katoomba.
Severe thunderstorms could also hit Sydney late this afternoon.
The NSW State Emergency Service (SES) has urged people to prepare for the storm by moving cars away from trees, securing loose items and staying indoors.
It comes as another round of wet and stormy weather is on the way for northern and eastern Australia next week.
Weatherzone said there will be several days of rain and thunderstorms starting Monday through to the end of the week.
“Rainfall will be hit and miss and totals are likely to vary quite a lot from place to place,” Ben Domensino from Weatherzone said.
“Some areas could receive more than 50mm, while others will miss out altogether.”