The purpose of this research work is to gain a better understanding of the nanostructural properties of Molybdenum (Mo) thin films’ porosity, nanovoid heterogeneity and provide detailed quantitative data on voids volume fractions, sizes, shapes, and their preferred orientations as the growth sputtering pressure changes systematically. This knowledge shall assists in optimizing Mo film nano- and micro-structural properties as desired for solar cells applications. Therefore, two separate series of Mo thin films (∼ 0.7 μm thick) were deposited on high purity (99.999) Al-foil (10 μm thick), and Si/SiO2 substrates using direct-current (DC) planar magnetron sputtering. The sputtering pressure was varied from 0.8 mT to 12 mT, with a sputtering power density of 1.2 W/cm2. High-Resolution Scanning Electron Microscopy (HRSEM) was used to examine the Mo films’ morphology. Whereas, the Mo films’ bulk resistivity was calculated from the films’ thickness and average sheet resistance measurements using Dektak Surface Profilometer, and Four Point Probe method, respectively. Small Angle X-Ray Scattering (SAXS) technique was applied to examine the existence of nanovoids and its heterogeneity in the Mo-coated Al foils (Al/Mo). Moreover, the porosity of the Mo films as a function of sputtering pressure was studied by Transmission Electron Microscopy (TEM) on Mo-coated Si/SiO2 (Si/SiO2/Mo) substrates.