The simultaneous removal of phenol and selenite from synthetic wastewater was investigated by adopting two different co-culturing techniques using the fungus Phanerochaete chrysosporium and the bacterium Delftia lacustris. Separately grown biomass of the fungus and the bacterium (suspended co-culture) was incubated with different concentrations of phenol (0–1,200 mg/L) and selenite (10 mg/L). The selenite ions were biologically reduced to extracellular Se(0) nanoparticles (3.58 nm diameter) with the simultaneous degradation of up to 800 mg/L of phenol. Upon growing the fungus and the bacterium together using an attached growth co-culture, the bacterium grew as a biofilm onto the fungus. The extracellularly produced Se(0) in the attached growth co-culture had a minimum diameter of 58.5 nm. This co-culture was able to degrade completely 50 mg/L phenol, but was completely inhibited at a phenol concentration of 200 mg/L.