"We are very honoured and proud she has agreed to serve on the committee," Pelosi said of Cheney at a news conference on Thursday.
The House voted on Wednesday to set up the panel, despite opposition from nearly all Republican lawmakers in the chamber, reports xinhua news agency.
Cheney, who was recently dumped from House Republican leadership, was one of the only two party members who backed the select committee, criticising fellow party members for their continued embrace of former President Donald Trump.
Cheney said in a written statement she was honoured to serve on the panel.
"Congress is obligated to conduct a full investigation of the most serious attack on our Capitol since 1814. That day saw the most sacred space in our Republic overrun by an angry and violent mob attempting to stop the counting of electoral votes and threatening the peaceful transfer of power.
"Those who are responsible for the attack need to be held accountable and this select committee will fulfil that responsibility in a professional, expeditious, and non-partisan manner," said Cheney.
Her removal from the REpublican leadership came after she voted to impeach Trump for inciting the Capitol riot, as well as her unabated denunciation of the former president's election-related claims.
Congressional Republicans have said Cheney's anti-Trump stance has hampered the party's ability to send a coherent message at a time when the 2022 midterm elections draw near.
In her announcement on Thursday, Pelosi said that the chair of the select committee will be Democratic Representative Bennie Thompson, currently chief of the House Homeland Security Committee that has already been investigating the insurrection.
Pelosi's other picks for the select committee are solely Democrats: House Administration Committee Chairwoman Zoe Lofgren, House Intelligence Committee Chairman Adam Schiff, Representative Pete Aguilar, Representative Stephanie Murphy, Representative Jamie Raskin, and Representative Elaine Luria.
According to the rules governing the panel, five members will be appointed by House Minority Leader Kevin McCarthy in consultation with Pelosi, meaning the latter could potentially veto McCarthy's choices.
McCarthy has not said whether he will cooperate with the select committee's member selection process.
CNN reported Wednesday that McCarthy threatened to strip any Republican member of their current committee assignments if they accept an offer from Pelosi to serve on the select committee.