Published Thursday, 20 September 2012
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The collection features everything from postcards and photographs to silverware, period magazines and firearms - all on show to the public for the first time.
It even includes the pen used by Sir Edward Carson to sign the Ulster Covenant.
Many of the objects are directly connected to key events and personalities associated with the historic signing, like Carson, John Redmond, Fred Crawford and James Connolly.
It is part of the 'The Ulster Crisis: Irish Home Rule and the Ulster Covenant 'exhibit, which looks at unionist and nationalist politics of the time in the context of the wider world and contemporary issues, such as the changing role of women and workers' rights.
William Blair of National Museums NI said: "The exhibition marks, not only the centenary of the signing of the Ulster Covenant, but also examines the much broader political and cultural context of this remarkable era leading up to the start of the First World War.
"Highlights include an original copy of the Scottish Solemn League and Covenant of 1643 (an inspiration for the 1912 Ulster Covenant), a ticket for a pro-Home Rule meeting at Celtic Park attended by Winston Churchill and John Redmond, as well as the only surviving poster of the Proclamation signalling the establishment of an Ulster Provisional Government should Home Rule become law."
Meanwhile a celebration will take place in the grounds of Stormont on Sunday 29 September to mark the centenary of the Ulster Covenant.
The Orange Order said it expects thousands of people to gather for the event in east Belfast following a parade through the city, with music, games and entertainment put on.
Grand Master of the Grand Orange Lodge of Ireland, Edward Stevenson said: "We expect the event on September 29 to be an occasion to remember and one worthy of the centenary.
"In our view, the Covenant anniversary will be about commemorating our forefathers and their belief in common values enshrined in the Union. We look forward to coming together as a community to do so."
The display at the Ulster Museum will run until 2014.