Former US president Bill Clinton and ex-Democratic Unionist Stormont first ministers Peter Robinson and Arlene Foster are set to attend.
Irish President Michael D Higgins and his predecessor, Mary McAleese, will also be at the Requiem Mass for the Sinn Fein veteran, as will Taoiseach Enda Kenny.
Mr McGuinness’s beloved Bogside neighbourhood will come to a standstill during this afternoon’s service at the Long Tower church.
The politician died from a rare heart condition on Tuesday aged 66.
It is set to be an extraordinary day of mourning in Derry.
Hours before Mr McGuinness’s funeral, the same church will witness the funeral of popular Derry City FC captain Ryan McBride, 27, who was found dead in his bed on Sunday.
Mr McGuinness’s death came in the midst of a political crisis at Stormont, with talks ongoing to form a new powersharing executive following the acrimonious collapse of the last administration.
Politicians from both sides of the region’s community divide will attend his funeral.
Ulster Unionist leader Mike Nesbitt will join DUP leaders past and present Mr Robinson and Mrs Foster. Their attendance will be seen as symbolically significant given Mr McGuinness’s IRA past.
Though thousands of supporters have lauded the legacy of Mr McGuinness, his death has drawn a very different response from many victims of the IRA, with some bereaved relatives not prepared to forgive him for his paramilitary involvement.
On Wednesday, political leaders at Westminster and Belfast commended his contribution to the peace process.
Prime Minister Theresa May told parliament she could never condone the ex-IRA commander’s violent past but she credited his “indispensable” role in moving the Republican movement away from armed conflict.
At a special session of the Stormont Assembly, Mr McGuinness’s Sinn Fein successor, Michelle O’Neill, paid an emotional tribute, while Mrs Foster acknowledged that Northern Ireland would “never see his like again”.
Mrs O’Neill told the Assembly her heart was broken yet bursting with pride.
“The legacy that Martin wished was for a better future based on equality and measured by the joy and laughter of all of our children,” she said.
“So, on behalf of Sinn Fein I rededicate our party to completing his life’s work and to living through his legacy.”
Mrs Foster said Mr McGuinness’s legacy was “complex and challenging”.
“Things have fundamentally changed since I was growing up in the ‘70s and ‘80s and changed immeasurably for the better, and Martin McGuinness did play a role which I will always condemn in the ‘70s and ‘80s, but I also have to acknowledge the role that he played over this last decade and more in government in Northern Ireland,” she said.
Mr McGuinness completed an extraordinary political journey from an IRA leader in Derry to sharing power and a remarkable friendship with his erstwhile foe, DUP leader Dr Ian Paisley.
He also struck up a warm relationship with the Queen, whom he praised for her contribution to peace. She is to send a personal message to Mr McGuinness’s family.
Mr McGuinness’s last major act as a politician was to pull down the powersharing executive at Stormont when he resigned as deputy first minister in January in protest at the DUP’s handling of a green energy scandal