A thin film analysis system includes multi-technique analysis capability. Grazing incidence x-ray reflectometry (GXR) can be combined with x-ray fluorescence (XRF) using wavelength-dispersive x-ray spectrometry (WDX) detectors to obtain accurate thickness measurements with GXR and high-resolution composition measurements with XRF using WDX detectors. A single x-ray beam can simultaneously provide the reflected x-rays for GXR and excite the thin film to generate characteristic x-rays for XRF. XRF can be combined with electron microprobe analysis (EMP), enabling XRF for thicker films while allowing the use of the faster EMP for thinner films. The same x-ray detector(s) can be used for both XRF and EMP to minimize component count. EMP can be combined with GXR to obtain rapid composition analysis and accurate thickness measurements, with the two techniques performed simultaneously to maximize throughput.