Biocompatible and resorbable optical fibres emerge as promising technologies for in vivo applications like imaging, light delivery for phototherapy and optogenetics, and localised drug-delivery, as well as for biochemical sensing, wherein the probe can be implanted and then completely absorbed by the organism. Biodegradable waveguides based on glasses, hydrogels, and silk have been reported, but most of these devices rely on complex fabrication procedures. In this sense, this paper proposes a novel structured optical fibre made of agarose, a transparent, edible material used in culture media and tissue engineering. The fibre is obtained by pouring food-grade agar into a mould with stacked rods, forming a solid core surrounded by air holes in which the refractive index and fibre geometry can be tailored by choosing the agarose solution composition and mould design, respectively. Besides exhibiting practical transmittance at 633 nm in relation to other hydrogel waveguides, the fibre is also validated for chemical sensing either by detecting volume changes due to agar swelling/dehydration or modulating the transmitted light by inserting fluids into the air holes. Therefore, the proposed agarose-based structured optical fibre is an easy-to-fabricate, versatile technology with possible applications for medical imaging and in vivo biochemical sensing.