Lignocellulosic materials can significantly contribute to the development of composites, since it is possible to chemically and/or physically modify their main components, cellulose, hemicelluloses and lignin. This may result in materials more stable and with more uniform properties. It has previously been shown that chemically modified sisal fibers by ClO(2) oxidation and reaction with FA and PFA presented a thin coating layer of PFA on their surface. FA and PFA were chosen as reagents because these alcohols can be obtained from renewable sources. In the present work, the effects of the polymeric coating layer as coupling agent in phenolic/sisal fibers composites were studied. For a more detailed characterization of the fibers, IGC was used to evaluate the changes that occurred at the sisal fibers surface after the chemical modifications. The dispersive and acid-base properties of untreated and treated sisal fibers surfaces were determined. Biodegradation experiments were also carried out. In a complementary study, another PFA modification was made on sisal fibers, using K2Cr2O(7) as oxidizing agent. In this case the oxidation effects involve mainly the cellulose polymer instead of lignin, as observed when the oxidation was carried out with ClO(2). The SEM images showed that the oxidation of sisal fibers followed by reaction with FA or PFA favored the fiber/phenolic matrix interaction at the interface. However, because the fibers were partially degraded by the chemical treatment, the impact strength of the sisal-reinforced composites decreased. By contrast, the chemical modification of fibers led to an increase of the water diffusion coefficient and to a decrease of the water absorption of the composites reinforced with modified fibers. The latter property is very important for certain applications, such as in the automotive industry.