Between them, Opel and PSA, which makes Peugeot and Citroen cars, have three factories in Spain, which employ about 13,000 people in total.
De Guindos did not detail in a radio interview whether he had sought guarantees for jobs and labour agreements.
Other countries affected by the merger talks, including France, Germany and the United Kingdom, had previously raised alarms over whether it could affect workers, and have held talks with the car makers in recent weeks.
"For the Peugeot group, if this merger ends up happening, Spain is going to be very important ... and they are well aware of that," De Guindos told RNE radio, singling out Opel's factory in Zaragoza and Peugeot's in Vigo as key.
"They also raise another question, that the Spanish factories ... are the most productive," de Guindos said, adding that Spain was "well-placed."
He did not say who at PSA he had spoken to.
Spanish workers at PSA and General Motors factories have raised concerns over the acquisition talks in recent weeks, according to union sources.
Staff at PSA's smaller Villaverde factory in Madrid, where production is running at well below capacity, are especially worried, they added.
(Reporting by Sarah White; Editing by Greg Mahlich)
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