We are living in a very interesting moment with the emergence of new X-ray analytical tools that meet the tight requirements of inline metrology of ultrathin materials and multilayers stacks in highly demanding semiconductor environment. These tools, based on X-ray fluorescence or X-ray photoemission spectroscopy, combine multiple monochromatic primary energies along with angle-dependent capability, which extends the range of XPS to buried interfaces, improves the sensitivity of XRF analysis and permits to reveal and monitor elemental depth-distribution with industry-driven accuracy. We will illustrate the use of multi-energy X-ray tools to address the challenges of inline metrology of 2D transition metal chalcogenides, complex high-k metal gate stacks for advanced CMOS and innovative non-volatile memory.