In 2005, Stefaan De Wolf completed his Ph.D. at Katholieke Universiteit Leuven in Belgium, concurrently working with imec on crystalline silicon solar cells. Following this, he spent the period from 2005 to 2008 at the National Institute of Advanced Industrial Science and Technology (AIST) in Tsukuba, Japan. In 2008, he assumed the role of a team leader at the Photovoltaics and Thin-Film Electronics Laboratory at Ecole Polytechnique Federale de Lausanne (EPFL) in Neuchatel, Switzerland, overseeing activities related to high-efficiency silicon solar cells.

Since September 2016, Stefaan De Wolf has held the position of professor at the King Abdullah University of Science and Technology (KAUST) in Saudi Arabia. In this capacity, he focuses on advancing high-efficiency silicon and perovskite solar cells, as well as their combinations. His expertise lies in the science and technology of photovoltaics for terrestrial applications, emphasizing the fabrication of high-efficiency solar cells. He places particular emphasis on understanding interface structures and electrical contact formation, which are crucial aspects for both solar cells and electronic devices.

Stefaan De Wolf's research extends to applications in photovoltaics for hot climates and multi-junction solar cells, aiming to enhance the utilization of the entire solar spectrum for electricity generation. Notably, he has been recognized as a Clarivate Highly Cited Researcher since 2019.