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Porous carbohydrate materials such as tobacco shreds readily absorb moisture and become damp during processing, storage, and consumption (smoking). Traditional humectants have the ability of moisture retention but moisture-proofing is poor. <i>Polygonatum cyrtonema</i> Hua polysaccharide (PCP 85−1−1) was separated by fractional precipitation and was purified by anion exchange and gel permeation chromatography. The average molecular weight (Mw) of PCP 85−1−1 was 2.88 × 10³ Da. The monosaccharide composition implied that PCP 85−1−1 consisted of fucose, glucose, and fructose, and the molar ratio was 22.73:33.63:43.65. When 2% PCP 85−1−1 was added to tobacco shreds, the ability of moisture retention and moisture-proofing were significantly enhanced. The moisture retention index (MRI) and moisture-proofing index (MPI) increased from 1.95 and 1.67 to 2.11 and 2.14, respectively. Additionally, the effects of PCP 85−1−1 on the aroma and taste of tobacco shreds were evaluated by electronic tongue and gas chromatography–mass spectrometry (GC-MS). These results indicated that PCP 85−1−1 had the characteristics of preventing water absorption under high relative humidity and moisturizing under dry conditions. The problem that traditional humectants are poorly moisture-proof was solved. PCP 85−1−1 can be utilized as a natural humectant on porous carbohydrates, which provides a reference for its development and utilization.