With growing environmental concerns over synthetic polymers, natural polymeric materials, such as hemicellulose, are considered a good sustainable alternative. Curaua fibers could be an excellent source of biopolymer as they have a relatively high hemicellulose content (15 wt%) and only a small amount of lignin (7 wt%). In this work, hemicellulose was extracted by an alkaline medium using KOH and the influence of the alkali concentration, temperature, and time was studied. A hemicellulose film was produced by water casting and its mechanical, thermal, and morphological properties were characterized. The results show that the best method, which resulted in the highest hemicellulose yield and lowest contamination from lignin, was using 10% (w/v) KOH concentration, 25 °C, and time of 3 h. The hemicellulose film exhibited better thermal stability and elongation at break than other polymeric films. It also exhibited lower rigidity and higher flexibility than other biodegradable polymers, including polylactic acid (PLA) and polyhydroxybutyrate (PHB).