Stratospheric airships are promising aircraft, usually designed as a non-rigid airship. As an essential part of the non-rigid airship, the envelope plays a significant role in maintaining its shape and bearing the external force load. Generally, the envelope material of a flexible airship consists of plain-weave fabric, composed of warp and weft fibre yarn. At present, biaxial tensile experiments are the primary method used to study the stress–strain characteristics of such flexible airship materials. In this work, biaxial tensile testing of UN-5100 material was carried out. The strain on the material under unusual stress and the stress ratio were obtained using Digital Image Correlation (DIC) technology. Also, the stress–strain curve was corrected by polynomial fitting. The slope of the stress–strain curve at different points, the Membrane Structures Association of Japan (MSAJ) standard and the Radial Basis Function (RBF) model were compared to identify the stress–strain characteristics of the materials. Some conclusions on the mechanical properties of the flexible airship material can be drawn and will play a significant role in the design of such envelopes.