Much of Sydney reached its peak temperature at about 3 p.m., with the city's west bearing the brunt of the heat, reports the Guardian.
Richmond reached 46.3 degrees Celsius just after 2.30 p.m., while the temperature in Bankstown exceeded 45 degrees Celsius.
A severe fire danger rating was issued for the greater Sydney regiony, while much of the rest of the state has a "very high" rating.
Total fire bans are in place for Sydney and the Hunter region.
The Bureau of Meteorology said cooler conditions were expected to reach coastal areas later in the day.
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