The use of untreated natural fibers to reinforce cementitious composites improves their environmental friendliness, resulting in a more sustainable material. Moreover, the influence of the untreated natural fibers on the hydration process of Portland cement composites presents some uncertainties. According to the literature, the most usual tests to analyze the degree of hydration of cement composites are the differential thermal and thermogravimetric analyses (TGA/dTGA). Several authors propose to analyze data methods to establish the degree of hydration of cement composites. This paper presents the TGA/dTGA test carried out on mortar samples with and without fibers at age 2, 3, 7, 14, and 28 days. The degree of hydration was calculated according to Bhatty’s method. To characterize the raw materials, the quantitative chemical was determined using scanning electron microscopy and energy dispersive X-ray spectroscopy (SEM–EDX). The main findings of this study were that the presence of untreated natural hemp fibers in the OPC composites increased the hydration degree by 9%. The presence of fibers affected the formation of several components. Thus, their presence increased the formation of monosulphate, reduced portlandite, did not affect ettringite, and increased the formation of calcite, thereby improving the sustainable footprint due to the increased CO2 fixation.