The degree of crystallinity in cellulose significantly affects the physical, mechanical, and chemical properties of cellulosic materials, their processing, and their final application. Measuring the crystalline structures of cellulose is a challenging task due to inadequate consistency among the variety of analytical techniques available and the lack of absolute crystalline and amorphous standards. Our article reviews the primary methods for estimating the crystallinity of cellulose, namely, X-ray diffraction (XRD), nuclear magnetic resonance (NMR), Raman and Fourier-transform infrared (FTIR) spectroscopy, sum-frequency generation vibrational spectroscopy (SFG), as well as differential scanning calorimetry (DSC), and evolving biochemical methods using cellulose binding molecules (CBMs). The techniques are compared to better interrogate not only the requirements of each method, but also their differences, synergies, and limitations. The article highlights fundamental principles to guide the general community to initiate studies of the crystallinity of cellulosic materials.