The application of natural fibres as polymer reinforcement is of extreme interest, especially in combination with biodegradable polymers. Such “green” composite represent a step forward to eco-design and environmentally friendly applications. The use of biodegradable polylactic acid (PLA) on the basis of renewable resources in addition to the biodegradable polyvinyl alcohol (PVA) on petrochemical basis is compared in this study with the application of polypropylene (PP) as a surrounding matrix for sisal fibres. According to the law of similarities, the chemically similar structure of natural fibres and PVA and PLA provides stronger fibre-matrix bonding characteristics compared to PP. This was experimentally validated applying single-fibre pull-out tests, where the effect of improved bonding is further investigated in terms of tensile and impact composite behaviour. SEM investigation was further applied to describe failure modes of natural fibre composites.