Chris Smith, the Secretary of State for Culture, said yesterday that Rubens' painting of Teresa of Avila's vision of a Dove will hang in the Fitzwilliam Museum, Cambridge, and the Millais will go to the Tate Gallery. It has not yet been decided where the sculpture will go.
A spokeswoman for the Tate said the gallery has other works by Sir John Everett Millais but that Mariana is a "wonderful" example. "It epitomises the style of Pre-Raphaelites and Millais did it during his most important period in the 1850s."
Millais painted Mariana after reading Tennyson's poem of the same name. The poem was, in turn, based on a character in Shakespeare's Measure for Measure. It was first exhibited at the Royal Academy in 1851 and a verse of Tennyson's poem was inscribed on the reverse of the frame.
A spokeswoman for the Department of Culture said the Government had accepted the painting in lieu of pounds 4.2m of inheritance tax.
"If someone inherits a lot of valuable items and ends up with a very large inheritance tax bill, they can offer items to the nation in lieu of paying that tax," she said. "But it has to be something of pre-eminent importance and must satisfy the Government of its worth.
"Once it has been accepted then galleries and museums have to bid for it and, unless the family has specifically asked for it to be displayed in a certain place, then the Government decides where it will go."
The Rubens painting was accepted in lieu of pounds 420,000 tax and the Henry Moore was valued at pounds 63,000. The Ballad Seller, by the 18th-century painter Henry Walton, with a tax value of pounds 115,000, was also accepted under the scheme.
The Government is also taking an archive that once belonged to Clive of India, and which includes a record of his three Shropshire estates. The huge archive, described as an outstanding history of the country, occupies about 900 boxes and includes 1,000 maps and plans. By giving it to the nation, his family has saved pounds 116,471 inheritance tax.
"I am very pleased that these pre-eminent items have been saved for the nation," Mr Smith said yesterday. "The key element that links the objects together is their outstanding interest and importance to our heritage."