The commissioned artwork, by Peter Howson, shows Artaban following the star to Bethlehem.
It will be sold at auction in the New Year with the proceeds shared between the Children's Hospice Association Scotland (Chas), CLIC Sargent, Scottish Catholic International Aid Fund (Sciaf) and Combat Stress, the charity chosen by the artist.
Alex Salmond's Christmas card has raised £148,000 for charities in Scotland since it was launched in 2007, through sales of the original artwork and limited edition prints.
Artaban is a "hugely appropriate" work for his card, Mr Salmond said.
"The legend of Artaban, or the fourth wise man, is based on a novel by Henry van Dyke. It tells the tale of a Persian scholar who, delayed by helping the vulnerable, follows the star to Bethlehem but arrives just too late to herald the birth of the Christ child. Thirty years on in Jerusalem, at Passover, Artaban is still searching.
"Now an old man, he parts with the last of his three gifts to Jesus, a sapphire, a ruby and a pearl, to save a young girl from slavery. However, in a dying vision, Artaban is comforted that his devotion to the distressed has secured him entrance to the kingdom of heaven.
"The story reminds us that hope, faith and self-sacrifice are at the centre of the order of things.
"I am very grateful to Peter for donating this outstanding painting. As you might expect it's a typically powerful image, unmistakeably Howson, and I am sure it will go on to make a significant figure for these four very good causes at auction next year."
Each charity will be given a series of limited edition prints of the work to help with their fundraising efforts.
The artwork was unveiled today in front of Mr Howson, Mr Salmond and representatives of the charities at an event at Malcolm Sargent House in Prestwick, the holiday home run by CLIC Sargent for young people and their families who are coping with cancer.
Mr Salmond officially opened the home's playroom earlier this year.
Lucy Caldicott, CLIC Sargent's director of fundraising, said: "We are grateful for his support and hope the card will raise money to help children and young people with cancer throughout the festive season."
Chas and Sciaf say they are honoured to be chosen to benefit from the card.
Andrew Cameron, chief executive of Combat Stress, said: "For most of us the realities of war are far removed from our everyday lives. It means a great deal for a war artist like Peter Howson, who served in the Royal Highland Fusiliers and bore witness to the horrors of war in Bosnia and Kosovo, to support us.
"Peter Howson and the First Minister are signalling, in a very personal way, the importance of specialist treatment for veterans suffering psychological wounds from their service."
The other artists who have taken part in the Christmas card initiative since its launch are John Lowrie Morrison, the late John Bellany, Gerard Burns, Jack Vettriano, Alasdair Gray and Dame Elizabeth Blackadder.