On her first visit to Egypt since being appointed as top US diplomat in January, Rice will first talk with Mubarak in the Red Sea resort of Sharm el-Shaikh on Monday.
She is then expected to deliver a policy speech at the American University in Cairo before meeting several opposition politicians.
Among them will be Ayman Nour, the leader of the opposition Ghad Party whose jailing by the authorities had prompted Rice to cancel a trip to Egypt in March.
Pressure on ally
She is expected to prod the Egyptian government to expand political freedoms but faces reformers' calls to exert more pressure on the key US Arab ally.
The Bush administration, which needs Cairo's help to bring Israelis and Palestinians closer to peace, has tempered its criticism of Egypt's steps towards democracy despite widespread condemnation that its election reform this year is a sham.
Rice met Palestinian leader
Mahmoud Abbas on 18 June.
"I will have a chance when I'm in Egypt to talk more about the need for reform, about the need for the Middle East and Middle Eastern leaders to hear the voices of their people and their people's desire for reform," Rice said at a news conference in Jordan on the eve of her visit to Egypt.
This year, US President George Bush urged Egypt - along with Saudi Arabia, which Rice will also visit on Monday - to lead democratic reforms in the Arab world.
Change in policy
In a policy shift that evolved after the 11 September 2001, attacks, Bush pledged to make democracy a central plank in all bilateral relations in the belief that long-term US interests were best served if freedom were spread.
"Very often people talked about the Middle East somehow being different, that what we needed to worry about in the Middle East was stability," Rice said on Sunday.
"And what we learned is that we were getting neither stability nor liberty and freedom; we were getting instead a growth of extremism because people did not have channels through which to express themselves politically," she said.
The state secretary is to meet
Ghad Party leader Ayman Nour
But the Bush administration's different standards for its allies and foes in the region could hurt her credibility in a region already sceptical of any US moral authority.
Mubarak's plan to hold multiparty presidential elections has been criticised by Egyptian and foreign analysts who think it sets too high a bar for independent candidates.
Rice last week said the change was an important first step but more needed to be done.
The secretary of state started her first major tour of the Middle East on Saturday and has talked with Israeli, Palestinian and Jordanian leaders. Her next stop will be Saudi Arabia, before attending a conference on Iraq in Brussels.