"The European Union is determined to help Myanmar pursue the path of peace, democracy and sustainable development; building up trade and investment, respecting human rights and fundamental freedoms and rebuilding relations with the international community," she said in a statement.
Ashton heads Wednesday to Myanmar to co-chair the first-ever EU-Myanmar task force aimed at facilitating the former junta's transition to a democratic country.
Myanmar earned international praise for holding general elections in 2010. Its political progress has been overshadowed by conflicts with the various ethnic groups fighting for more autonomy in a country known formerly as Burma.
Ashton is scheduled to meet with Myanmar ministers and Aung San Suu Kyi, an opposition leader and Nobel Peace Prize laureate who secured a seat in Parliament in by-elections in 2012.
The European Commission said both sides are expected to sign a series of draft agreements on private sector development.
International human rights groups have expressed concern about opening Myanmar up for investment opportunities. They say sanctions pressure was what encouraged Myanmar to reform in the first place.