Gold and silver nanoparticles (NPs) are shown to exert a positive effect on the chemiluminescence (CL) reaction of permanganate aldehydes. Interestingly, between various shapes examined, Au nanoprisms have the highest beneficial effect. This effect is even more notable in the presence of sodium dodecyl sulfate (SDS) surfactant. UV-vis spectra and transmission electron microscopy were used to characterize the NP shapes and sizes. Furthermore, it was observed that iron(III) ions can slightly increase CL emission of this system. This intensification is very effective in the presence of fluoride ions (F(-)). These observations form the basis of the method for the high sensitive determination of F(-) in the 6-1200 nmol L(-1) concentration range, with a detection limit of 2.1 nmol L(-1). The proposed method has good precision and was satisfactorily used in the selective determination of low concentrations of fluoride ion in real samples.