In response, Mary Lou McDonald said the decision to attend is "very wrong".
Foreign Affairs Minister Simon Coveney and Chief Whip Jack Chambers will represent the government at an event to mark the centenary of partition in Northern Ireland this month.
The announcement comes following President Michael D Higgins last month
turning down an invitation to the ceremony, which is to take place at St Patrick's Church of Ireland Cathedral in Armagh on 21 October and will be attended by the Queen of England.
The President told reporters at the time that what was initially delivered as an invitation to a religious service had devolved into a political statement and thus it would be "inappropriate" for him to attend.
He also took issue with the invite referring to him as the President of the Republic of Ireland, when, in fact, he is the President of Ireland.
In a statement on Thursday, the government said: "The government has today considered the invitation which it received from The Church Leaders Group (Ireland) to the Service of Reflection and Hope which the Group is organising in Armagh later this month.
"In considering the invitation, the government noted that its role in this matter is clearly distinct from that of the President.
"In that regard, the government reiterates its full support and understanding for the decision made by President Higgins with regard to his attendance at the event.
"The decision was quite properly made by the President and was based on concerns that he had consistently expressed.
"Cognisant of that important distinction and in recognition also of the spirit and intentions of the Church Leaders in organising the event, the government has decided that it will be represented at the event by the Minister for Foreign Affairs and by the Government Chief Whip."
Following the announcement, Sinn Féin leader Mary Lou McDonald wrote on Twitter that the government should follow the lead of President Higgins.
"No member of the Irish Govt should participate in the commemoration of partition - a catastrophic event for Ireland," she wrote.
"The decision to attend is wrong. Very wrong."
https://twitter.com/MaryLouMcDonald/status/1446209443344101386
Main image via Julien Behal Photography / RollingNews.ie
