Sisal fibre reinforced composites, one class of a broad range of eco-composite materials, were studied in connection with the effects of fibre surface treatment on their fracture-mechanical properties. Previous investigations on sisal fibre and its composites have been fully reviewed [1], which provided an impetus for this research. Two fibre surface treatment methods, chemical coupling based on silane and oxidization based on permanganate and dicumyl peroxide, together with untreated sisal fiber composites were used to set up different levels of interface bonding strength. The interface effects on the mechanical properties and fracture toughness of sisal fibre reinforced vinyl-ester composites were completely assessed based on the test results obtained and theoretical analyses. Many aspects of studies reported in this paper are original, such as single fiber pull-out tests and toughness evaluation of sisal composites aided by scanning electron microscopy. The results showed that fibre surface treatment could improve interfacial bonding properties between sisal fibre and vinyl-ester resin. These in turn influenced the fracture-mechanical characteristics of this class of ecocomposites.