The mechanism of carbon nanotube (CNT) alignment during stretching was examined by the in situ characterization of carbon nanotube networks (CNTNs) under tensile strains using X-ray and Raman scattering techniques. A method of quantifying the inhomogeneous alignment of macroscopic CNTNs is explored based on bulk property measurements of their electrical anisotropy and X-ray diffraction diagrams. The results show that the process of stretch-induced alignment of CNTNs included straightening the waviness of the long nanotube ropes, as well as the self-assembling and denser packing of the nanotubes. For samples at a strain of 40%, the fraction of aligned nanotubes was as high as 0.85. The aligned fraction of CNTs serves as an important parameter for the quality control of the alignment process and numerical simulations of structure–property relationships of CNTNs and their composites.