The production of agricultural residues causes environmental pollution, especially in regions with intensive horticultural production. The solution is to maximise the use of residues, applying the 'zero waste' model and using them to develop construction materials. Natural fibres used to reinforce materials have environmental and economic benefits due to their low cost. This research presents an innovative characterisation using an inverted-plate optical microscope, a high-resolution scanning electron microscope (HRSEM) and a 3D X-ray microscope. A physico-mechanical and chemical characterisation of horticultural fibres was also conducted. The fibres analysed were those produced in the highest quantities, including those from tomatoes, peppers, zucchinis, cucumbers and aubergines. The viability of these natural fibres for use as reinforcements in biocomposites was investigated. The analysis centred on studying the microstructure, porosity, chemical composition, tensile strength, water absorption and environmental degradation of the natural fibres. The results showed a porosity ranging from 47.44% to 61.18%, which contributes to the lightness of the materials. Cucumber stems have a higher tensile strength than the other stems, with an average value of 19.83 MPa. The SEM analysis showed a similar chemical composition of the scanned fibres. Finally, the life cycle of the materials made from horticultural residue was analysed, and negative GWP (global warming potential) CO2eq values were obtained for two of the proposed materials, such as stabilised soil reinforced with agricultural fibres and insulation panels made of agricultural fibres.