In 2009, a cement plant located in Alcanar (South Catalonia, Spain) started co-processing a special kind of refuse-derived fuel (RDF) called ENERFUEL™. In April 2014 and 2017, 5 and 8 years after RDF co-processing, the concentrations of metals and metalloids (As, Cd, Co, Cr, Cu, Hg, Mn, Ni, Pb, Sb, Tl, V and Zn) and PCDD/Fs were measured in samples of soils, herbage and air collected in the vicinity of the facility. The comparison of the current concentrations with those obtained in a baseline study (2008), when fossil fuels were used solely, has shown that the environmental concentrations of metals, metalloids and PCDD/Fs were not significantly modified. The concentrations of metals, metalloids and PCDD/Fs in soil, vegetation and air of Alcanar are in the low part of the ranges found around other cement plants in Catalonia (in general, below 50th percentile). Non-carcinogenic risks due to exposure to metals, metalloids and PCDD/Fs were lower than the safety value (HQ<1). In turn, carcinogenic risks were below the 10−5 Spanish threshold. The present results corroborate that, from an environmental point of view, the use of wastes as alternative fuels (AF) in a cement plant, which is operating with suitable technical conditions, is a good option for waste management. It contributes towards overcoming challenges such as climate change and fossil fuel depletion, while utilizing principles of circular economy.