A new homogeneous heteropolysaccharide (CMSPA90-1) was purified from bergamot by DEAE sepharose fast flow and Sephadex G-75 columns, and was shown to have a molecular weight of 17.6 kDa. Its chemical structure was elucidated by acid hydrolysis and methylation analysis, along with high-performance anion-exchange chromatography, Fourier transform infrared spectroscopy coupled with gas chromatography-mass spectrometry, NMR spectroscopies, the Congo red test, and circular dichroism. CMSPA90-1 consisted of a pyranoside and funanside with branches containing α- and β-configurations simultaneously. Arabinose and glucose might form an arabinoglucan backbone. The ultrastructure of CMSPA90-1 was further characterized by scanning electron microscopy (SEM) and atomic force microscopy (AFM). The results of thermogravimetric analysis (TGA) revealed that CMSPA90-1 had good thermal stability. The results of DPPH˙ and ABTS ~(+) ˙ radical scavenging assays indicated that CMSPA90-1 exhibited free-radical-scavenging properties. Otherwise, CMSPA90-1 could promote the proliferation of mouse splenocytes and the neutral red phagocytosis of RAW264.7 cells, which indicated that CMSPA90-1 could be researched and developed as one of the potential functional foods or natural medicines.
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