More than two dozen portraits will go on display at his presidential library in Dallas in April at an exhibit titled "The Art of Leadership: A President's Personal Diplomacy."
The exhibit "will explore the relationships that President George W Bush forged with world leaders to shape international policy and advance American interests abroad," the library said in a statement.
"Portraits will be accompanied by artifacts, photographs, and personal reflections to help illustrate the stories of relationships formed on the world stage."
He has refrained from the high-profile charitable and political work that marked the retirements of predecessors Jimmy Carter and Bill Clinton.
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Instead, he has lived a quieter life in Dallas with his wife Laura and took up painting after learning how the hobby had absorbed former British prime minister Winston Churchill.
He acknowledged the limitation of his skills in an interview last year in which he said he has help from a "patient" instructor and paints daily.
"I look at colours differently, and I see shadow.