In this study, we employed the metal-enhanced fluorescence (MEF) method for the detection of polycyclic aromatic hydrocarbons (PAHs) in diesel oil emulsions in artificial seawater. Silver nanoparticles with an average diameter of 80 nm were immobilized onto silanized quartz as MEF substrates. Excited by illumination at 355 nm, a 4.6-fold increase in the fluorescence signals of PAHs was recorded when MEF substrates were used. The finite-difference time-domain (FDTD) method was used to provide mechanistic insights into the fluorescence enhancement. Monitoring water pollution has environmental significance and MEF spectroscopy is finding direct applications in this field.