With more than a half-century in operation, the industrial chemical complex of Estarreja (ICCE) in northern Portugal has left serious environmental liabilities in the region. Although protective measures were implemented, soils, surface, and groundwater contamination caused by persistent pollutants are still prevalent. This study presents data from several geophysical and hydrochemical campaigns carried out to monitor groundwater contamination in the Estarreja region over a period of 30 years. Both geophysical and hydrochemical data showed a good agreement and revealed an important anomaly caused by groundwater contamination (high levels of Na, Cl, SO4, and Fe, among others) in 2006–2007, likely caused by the remobilization of waste pollutants (roasted pyrites, soils, and sludge) during their deposition in a sealed landfill (operating between 2003 and 2005). More recently, in 2016, this impact persists, but was more attenuated and showed a general migration pattern from E to SW according to one of the main groundwater flow paths. Groundwater flow in this region has a local radial behaviour. Drainage effluent systems, such as ditches and buried pipes formerly used by ICCE, are also likely to contribute to some contamination “hotspots”. Finally, the results obtained by the combined use of these two approaches allowed for the delineation of the contamination plume for future monitoring.