The complex plant cell wall heteropolysaccharide xylan, and its breakdown products xylo-oligosaccharides and xylose, are value-added compounds with a plethora of potential applications in diverse areas. They are nonetheless currently poorly exploited, with a major bottleneck being the unavailability of efficient, low-cost, high-yield production processes. The major objective of the present study is to identify and characterise a high-yield process for the preparation of highly pure xylan/XOS products from the macroalga . Currently, most xylan is extracted from land-sourced lignocellulosic feedstocks, but we take advantage of the high xylan content, xylan aqueous solubility, lignin-free nature, weakly linked cell wall matrix, and sustainability of the macroalga to identify a simple, sustainable, high-yield, novel-xylan-structure extraction process. This is composed of five steps: alga oven drying, milling, aqueous extraction, centrifugation, and dialysis, and we show that the alga preservation step plays a critical role in component extractability, with oven drying at high temperatures, 100 °C, enhancing the subsequent aqueous extraction process, and providing for xylan yields as high as 80% of a highly pure (90%) xylan product. The process developed herein and the insights gained will promote a greater availability of these bioactive compounds and open up their application potential.