To address spoilage and quality deterioration, this study evaluated the synergistic effects of the electrostatic field (EF) combined with packaging (polyethylene, PP; vacuum, VP; modified atmosphere, MAP) on the preservation of Yorkshire pork (hind leg) during controlled freezing-point storage (−2.0 ± 0.5 °C) for 32 days. The results showed that EF treatment significantly enhanced the water-holding capacity of PP-packaged pork, reducing storage loss by approximately 37.89% by day 32 (p < 0.05), and inhibited microbial growth, maintaining total viable counts below 6.00 log₁₀ (CFU/g) (p < 0.05). EF also reduced the relative abundance of spoilage organisms such as Pseudomonas. A synergistic effect between EF and VP/MAP was observed in the optimization of the microbial community structure. Spearman correlation analysis revealed that Pseudomonas abundance was positively correlated with TVB-N and storage loss, linking it mechanistically to quality deterioration. Furthermore, VP and MAP alone were superior in delaying lipid oxidation (TBARS < 0.5 mg MDA/kg) and maintaining color stability. This study provides key process parameters and a theoretical basis for applying EF-coupled packaging in the industrial cold chain.