Gate-all-around (GAA) nanowire (NW) devices have long been acknowledged as the ultimate device from an electrostatic scaling point of view. The GAA architecture offers improved short channel effect (SCE) immunity compared to single and double gate planar, FinFET, and trigate structures. One attractive proposal for making GAA devices involves the use of a multilayer fin-like structure consisting of layers of Si and SiGe. However, such structures pose various metrology challenges, both geometrical and material. Optical Scatterometry, also called optical critical dimension (OCD) is a fast, accurate and non-destructive in-line metrology technique well suited for GAA integration challenges. In this work, OCD is used as an enabler for the process development of nanowire devices, extending its abilities to learn new material and process aspects specific to this novel device integration. The specific metrology challenges from multiple key steps in the process flow are detailed, along with the corresponding OCD solutions and results. In addition, Low Energy X-Ray Fluorescence (LE-XRF) is applied to process steps before and after the removal of the SiGe layers in order to quantify the amount of Ge present at each step. These results are correlated to OCD measurements of the Ge content, demonstrating that both OCD and LE-XRF are sensitive to Ge content for these applications.