Despite cellulose being the most abundant biopolymer on earth and an important commodity, there is a lack of deeper knowledge about its structure as well as faster and more efficient characterization techniques. This paper presents preparation of nanocellulose from bleached cellulose pulp of Eucalyptus by chemical and mechanical pre-treatments, while the cellulose was given treatment to obtain a great range of crystallinity index. The nanocellulose is characterized by X-ray diffraction to evaluate Segal's index while chemometric tools by TGA and DTA were used to predict Segal's index. DTA curves, along with multivariate statistical model, presented better result than TGA. The coefficient of variation and standard error of prediction for the proposed models using external validation samples were in the range of 0.91-0.96 and 4.18-8.71, respectively. These successful mathematical models are discussed by correlating them with the observed characteristics of cellulose. (C) 2016 Elsevier B.V. All rights reserved.