Grazing-exit electron probe x-ray microanalysis (GE-EPMA) was used for the quantitative analysis of films with thicknesses of 10 and 4 nm. First-order calibration curves were obtained for the determination of Ti and Cr over a wide range of concentrations. The results confirmed that matrix effects are negligible when the film thickness is below some critical value. The minimum detection limits were obtained at the small exit angles (0. 75 • for the 10 nm thick film on the gold and 0.53 • for the 4 nm thick film on the silicon substrate). Detection limits were improved by a factor of 6.5 under grazing exit conditions for the film with a thickness of 10 nm and by a factor of 2 for the film with a thickness of 4 nm, compared with detection limits obtained at 45 • .