Humberto Ramos's cover features Doctor Octopus, who has replaced Peter Parker as the Superior Spider-Man.
His artwork pays homage to Todd McFarlane's cover for the milestone Amazing Spider-Man #300.
Otto Octavius is currently residing in Peter Parker's body, while the final issue of the series saw the hero die in the sickly body of the villain.
Writer Dan Slott has received death threats regarding the storyline, the details of which leaked earlier in December.
Kevin Smith has predicted that the change will not last a year.
Amazing Spider-Man #700 has sold over 250,000 issues.
The second printing will arrive on January 9.