The movie - the 23rd in the series - sees Daniel Craig assume the role of 007 for a third time and will be given its world premiere at the Royal Albert Hall in London on October 23.
Charles, who will be accompanied by the Duchess of Cornwall, has asked for the screening to benefit charities that support members of the three intelligence agencies - the Secret Intelligence Service (MI6), the Security Service (MI5) and GCHQ.
Among those due to attend the premiere are Craig and Dame Judi Dench who returns as M, along with other stars such as Javier Bardem, Ralph Fiennes, Naomie Harris, Berenice Marlohe, Albert Finney and Ben Whishaw. Oscar-winning director Sam Mendes will also stride the red carpet.
The Bond movies celebrate a half century this year and Skyfall's premiere comes little over a fortnight after the 50th anniversary of the first bond film, Dr No, received its world premiere on October 5 1962.
Film bosses have tried to keep a lid on the plot for the movie, which is being released on October 26. However they have released tasters of the action in trailers with Bond's loyalty to his boss M tested to the limits. MI6 comes under attack and 007 has to trace and destroy the threat.
Producers of the film said: "We are thrilled His Royal Highness Prince Charles and the Duchess of Cornwall have agreed to attend the world premiere of our latest James Bond film, and are pleased this event will help raise funds to support the Prince's chosen charities."
