Polygonatum sibiricum (P. sibiricum) is an edible and medicinal plant resource, and its traditional processing can induce changes in chemical composition and affect product quality. To clarify the effects of different steaming and drying rounds on the physicochemical properties and non-volatile metabolite composition of P. sibiricum extracted liquor, liquor samples prepared from P. sibiricum subjected to 0-9 steaming and drying rounds were analyzed. The chroma, hue, pH value, soluble solid content, and the contents of polysaccharides, total flavonoids, total saponins, and total phenolics were determined. In addition, the non-volatile metabolites in samples subjected to 0–3 steaming and drying rounds were characterized using ultra-performance liquid chromatography coupled with quadrupole time-of-flight mass spectrometry (UPLC-Q-TOF-MS)-based untargeted metabolomics. The results showed that the chroma and hue of the extracted liquor gradually increased with increasing steaming and drying rounds, while the pH value decreased to 5.28 and the soluble solid content showed slight variation. The polysaccharide content decreased to 0.40 mg·mL?¹, whereas total flavonoids and total saponins exhibited an initial increase followed by a decrease. The highest total phenolic content (7.43 mg·mL?¹) was observed after three steaming and drying rounds. A total of 3809 non-volatile metabolites were annotated, mainly including amino acids and derivatives, organic acids, nucleotides and derivatives, and lipids. Significant differences in metabolic profiles were observed among samples with different steaming and drying rounds and differential metabolites were mainly associated with amino acid derivatives, phenolic compounds, and small peptides. These findings indicate that steaming cycles regulate the composition of non-volatile metabolites in P. sibiricum extracted liquor. This study provides a theoretical basis for optimizing steaming processing conditions and quality control of P. sibiricum Baijiu products.