The items are among 44 lots, still held directly by Bonaparte's descendents and estimated to be worth just under 1 million pounds ($1.3 million), to be auctioned in Sotheby's annual Treasures sale of decorative arts, the Guardian reported on Sunday.
Henry House, head of furniture and decorative arts at Sotheby's, described the miniatures as a family album from an era before photographs.
"These are intimate personal portraits that have been passed on within the family," he said.
"We see Napoleon's father, mother, brothers and sisters, and in-laws; it's a remarkable group of items being presented at the same time. These portraits are how they see themselves in the family, rather than how they want to be presented to the public."
House said that there was an enduring fascination for Napoleon nicknamed Boney by the English.
"He was a pretty amazing man who came to France as an immigrant, became emperor and had an incredible dynasty that stretched across Europe. There's an enduring mystery and romanticism about Napoleon, similar to that of a rock or film star who dies young."
Bonaparte was taken prisoner by the British, with whom he had sought asylum after the French turned against him following his defeat at the Battle of Waterloo in June 1815 and sent to the remote south Atlantic island of St Helena, reports the Guardian.
Among the personal effects he took with him were a collection of 33 mainly tortoise-shell snuff boxes, many set with portraits of close family members.
Two being sold this week portray Bonaparte's father, Carlo Maria Buonaparte, a descendent of minor Tuscan nobility who had moved to Corsica, and his mother Maria Letizia Bonaparte.
Another snuff box bearing Bonaparte's portrait was given to General Henri Bertrand, one of his most trusted aides, who joined him in exile on St Helena and was at his deathbed there on May 5, 1821.
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