Ashton, who is on her first visit to India as EU high representative for foreign affairs and security policy and the first vice president of the European Commission, held delegation-level talks with her Indian counterpart, External Affairs Minister S.M. Krishna.
She later called on Prime Minister Manmohan Singh.
Ahead of the next EU-India summit, the discussions were largely to firm up the agenda for the October meeting in Brussels.
According to sources, the situation in Afghanistan figured during the talks, where several EU nations have stationed troops to fight against the Taliban.
Security and defence cooperation was also on the agenda, with her delegation including EU's anti-terrorism coordinator, Gilles de Kerchove and head of EU military staff, General Ton Van Osch.
Besides, economics are at the core of relations, with both stressing the need to expedite talks on a new comprehensive trade and investment agreement.
India raised its concern about the seizure of some consignments of table grapes by European port officials for allegedly having residue of a specific banned chemical compound.
India has alleged that these were part of new non-tariff barriers being put up by the EU side.
India and Brazil have already gone to the World Trade Organisation against the seizure of generic medicines in transit through European ports.
The bilateral trade between the 27-nation bloc and India is estimated to be over $50 billion. The two sides agreed to double bilateral trade in another five years at the India-EU summit in Marseilles, France, in September 2008.
On Wednesday, Ashton will be meeting Overseas Indian Affairs Minister Vyalar Ravi and Home Minister P. Chidambaram. She will also give a public lecture on the EU foreign policy at India International Centre in the evening.