Daina Pelēce holds a Diploma in Engineering Economics, specialisation: customs management and tax administration, and a Master's Degree in Economics (International Economic Relations Management) from Riga Technical University. She worked as an auditor at "Rīgas Audits", Ltd from 1994 to 1998, was an expert of the Budget Department at the Ministry of Finance of the Republic of Latvia in 1998 and 1999, and was employed at the Internal Audit Department of the Treasury of the Republic of Latvia in 1999 and 2000.
Daina Pelēce started her career at Latvijas Banka in 2000 as a junior economist of the Monetary Policy Department. Her responsibilities included analysing Latvia's fiscal policy and budget indicators, and macroeconomic indicators of East European countries and new EU Member States, studying Latvia's labour market, participation in working groups, and research on the healthcare system of Latvia. Daina Pelēce is currently involved in analysing Latvia's foreign trade balance and external debt.