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With an annual production of about 5 million tons, Cajanus cajan (pigeon pea) generates at least 20 to 25 million tons of stems as residues. These residues are generally disposed of as waste leading to environmental pollution and loss of a valuable raw material. In this report, we demonstrate that the stems of pigeon pea could be used as a source for developing natural cellulose fibers. Fibers were extracted from the stems using only water and also with water followed by alkali treatment. Fibers with high strength (984 MPa) and elongation (3.4%) similar to the properties of flax fibers were obtained. The physical and morphological properties of the fibers were similar to the common fibers. The fibers had good thermal stability and showed potential to be useful for textile, composite, and other applications. Such applications will provide a considerably high value addition to the stems of C. cajan and also be a renewable and sustainable source for fibers.