The performance of sisal fibers in cement-based matrices is highly dependent on the interface efficiency between the fiber and the matrix. This behavior in turn is directly related to two main factors: the sisal fiber swelling tendency and fiber alkaline degradation. To enhance these properties and consequently the fiber–matrix adhesion, this study proposed the use of carboxylate styrene-butadiene rubber latex (XSBR) as a coating for sisal fibers. Different XSBR polymers and emulsions concentrations were adopted. The effects of this treatment on various properties of the fibers such as physical, chemical, and mechanical properties were studied. The physical properties of the modified fibers were investigated by means of scanning electron microscopy (SEM) and atomic force microscope (AFM) analyses. Also, changes in the moisture absorption capacity of the coated fibers were evaluated. To study the chemical influence of the polymer coating in the modified fibers, thermogravimetric analysis (TGA) and Fourier transform infrared spectroscopy (FTIR) techniques were adopted. Direct tensile and pullout tests were also assessed in natural and coated sisal fibers, to mechanically evaluate the modification in terms of fiber strength and adherence, respectively. The results evidenced the formation of a new polymeric layer around the fiber, responsible to reduce the water absorption tendency of the natural fiber. The increase in the fiber–matrix adhesion obtained in the pullout evaluation was attributed to the rougher superficial aspect of the modified fibers and increased chemical interaction between the polymer and the cementitious matrix. Moreover, it was proven that the polymeric layer reduced the fiber's alkaline degradation susceptibility resulting in a more stable sisal fiber.