Álvarez holds a doctorate in Economic and Business Science from the Universidad Complutense de Madrid, and taught Economics at the Spanish National Open University between 1977 and 1990; at the Escuela de Prácticas Jurídicas in Málaga (1981–1989); and at the Instituto de Estudios Fiscales (1981–1989).
In 1979 she joined the Spanish Tax Inspectorate, holding various roles within the Ministry of Finance and afterwards in the AEAT, the Spanish Revenue Service.
She was Chief Inspector of the Tax delegation to Málaga from 1987–1989, Director of Regional Economic Incentives (1989–1993) a Director of the Department of Financial Inspection of the National Tax Inspectorate.
Álvarez was an MP in the Andalusian parliament for the province of Málaga, and in August 1994 she was named Minister of the Economy and Revenue for the Junta de Andalucía, becoming a member of the second cabinet of Manuel Chaves.
During her time as a minister, neither of her two budgets were approved by the Parliament.
In 1996, after the regional elections, she was confirmed in her post by Chaves, subsequently focusing on the payment of Andalucía's public debt and autonomous finance.
In the subsequent elections, in March 2000, Chaves kept her as head of the Ministry of Economy and Revenue for the sixth Andaluz Parliament.