Bletilla strata polysaccharide (BSP) has been attracting increasing attention because of its numerous bioactive components. In this study, BSP was obtained by water-extraction and ethanol-precipitation, and its structure and synergistic interaction with xanthan gum (XG) were then investigated. BSP was identified as a highly linear polymer with a weight average molecular weight (Mw) of 323.7 kDa, whose ratio of mannose to glucose was 2.4:1.0. BSP had the backbone of →4)-β-Manp-(1→, →4)-β-Glcp-(1→, as well as a small amount of →3)-β-Manp-(1→, terminated by T-Manp residues. Moreover, it was also substituted by a small number of O-acetyl groups at C-3 position of →4)-Manp-(1→ residue. Despite the poor gelling ability of BSP itself, it could form a firm and thixotropic gel when mixing with xanthan gum (XG). Upon cooling, irrespective of the mixing ratio, all BSP/XG mixtures exhibited a steep increase in G′ at ∼60 °C, which was defined as the onset temperature of the synergistic gelation. On heating, all gels melted at 60 °C, without detectable thermal hysteresis. The most pronounced synergistic interaction occurred at BSP/XG ratio = 5:5. Overall, this study provides new knowledge about the structure of BSP and its synergistic interaction with XG. Especially, the thixotropy of the mixed gels may find usefulness in formulating easy-to-swallowing food products.