Coreless filament winding (CFW) is a novel fabrication technique that utilises fibre-polymer composite materials to efficiently produce filament wound structures in architecture while reducing manufacturing waste. Previous projects have been successfully built with glass and carbon fibre, proving their potential for lightweight construction systems. However, in order to move towards more sustainable architecture, it is crucial to consider replacing carbon fibre’s high environmental impact with other material systems, such as natural fibre. This paper evaluates several fibres, resin systems, and their required CFW fabrication adjustments towards designing and fabricating a bio-composite structure: the LivMatS Pavilion. The methods integrate structural design loops with material evaluation and characterisation, including small-scale and large-scale structural testing at progressive stages. The results demonstrate the interactive decision-making process that combines material characterisation with structural simulation feedback, leveraged to evaluate and optimise the structural design. The built pavilion is proof of the first successful coreless filament wound sustainable natural fibres design, and the developed methods and findings open up further research directions for future applications.