Having been brought on in place of the injured Muhamed Besic in the opening stages on Merseyside, Naismith rounded off a great move to head the hosts in front on 17 minutes.
After stand-in Chelsea 'keeper Asmir Begovic had denied Arouna Kone and James McCarthy with two brilliant saves, the Scotland international doubled the Toffees' tally with a low strike on 22 minutes.
Chelsea clawed themselves back into the game when Nemanja Matic's thunderous drive halved the deficit ten minutes before the interval.
But the Chelsea comeback failed to materialise as Naismith became the first player to score a hat-trick against Jose Mourinho in the Premier League with his third eight minutes from time.
The result condemns Chelsea to their worst league start since 1988, while Everton's first victory of the season sees them claim a long-awaited first home win since their defeat of Manchester United in April.
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