The London club were reported on Friday to have had a £50million bid for the Argentina striker rejected by the Serie A club.
Higuain only joined the Naples outfit from Real Madrid in July, but Mourinho was said to be weighing up an improved offer for a player he knows all about from his time at the Bernabeu.
Fernando Torres, Samuel Eto'o and Demba Ba have struggled for goals this season, but Chelsea boss Mourinho has denied Higuain is a target and reiterated that he is not planning to add to his strikeforce during the transfer window.
When asked if Chelsea had made a bid for Higuain, the Chelsea boss said: "No. He's a player that I know, but we cannot (sign him) because he's a player who moved from Real to Napoli six months ago.
"He's doing very well; he's adapting well to Napoli. They are a club that don't sell; they want to win the Scudetto and now they are in the Europa League they will want to win that.
"They don't want to sell Higuain, so there is nothing in that."
When asked if he will be looking to sign a striker this month, Mourinho added: "No, it is not a priority and not an option. A striker, 100 per cent no."
Mourinho also confirmed a desire to keep midfielder Juan Mata despite previously saying "my door is open" if the Spain international decides he wants to seek pastures new.
Mata was not happy with being substituted during Chelsea's win at Southampton on New Year's Day, but Mourinho wants the former Valencia man to remain at Stamford Bridge.
Manchester United have been linked with Mata, but, when asked if Chelsea would allow the playmaker to join another Premier League club, Mourinho said: "No. I keep saying I want him to stay; there is no offer.
"Today (Friday) he trained in a fantastic way. So I think he is focused more on what I told him after the game at Southampton, when I told him I don't want him to leave, and not focused on what I told journalists that the door is open. "
Kevin De Bruyne's future has also been the subject of much speculation, with Wolfsburg said to be leading the race for his signature.
Mourinho warned potential suitors that the midfielder will not be sold on the cheap.
He said: "We knows he fancies a move. I don't want him to leave but we have a couple of contacts made by other clubs. I don't know (if he'll go).
"If people think they can get our good players on sale, the sales finished in London yesterday."
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