Methods and systems for performing simultaneous X-ray Fluorescence (XRF) and small angle x-ray scattering (SAXS) measurements over a desired inspection area of a specimen are presented. SAXS measurements combined with XRF measurements enables a high throughput metrology tool with increased measurement capabilities. The high energy nature of x-ray radiation penetrates optically opaque thin films, buried structures, high aspect ratio structures, and devices including many thin film layers. SAXS measurements of a particular location of a planar specimen are performed at a number of different out of plane orientations. This increases measurement sensitivity, reduces correlations among parameters, and improves measurement accuracy. In addition, specimen parameter values are resolved with greater accuracy by fitting data sets derived from both SAXS and XRF measurements based on models that share at least one material parameter. The fitting can be performed sequentially or in parallel.