The behavior of Scots pine (Pinus sylvestris L.) polysaccharides was studied during modified kraft pulping processes of wood meal by polysulfide (K-PS) and polysulfide anthraquinone (K-PSAQ) at the hydroxide ion concentrations of 0.50 and 1.55 M [OH-] with a high liquor-to-wood (L/W) ratio of 200. The high L/W ratio was selected for avoiding diffusion phenomena and to be able to focus on the chemistry of polysaccharides. A comparison with the kraft process reference at 160°C revealed a substantial increase in pulp yield (6–7% in K-PS pulping and 7.5–10.5% in K-PSAQ pulping) mainly attributed to galactoglucomannan (GGM) stabilization. Due to the rapid delignification rate at 1.55 M [OH-] concentration, the temperature could be lowered from 160°C to 130°C without a notable prolongation of cooking time. In K-PS pulping at 130°C, no additional GGM stability was observed compared to 160°C, whereas cellulose and arabinoxylan preservation was improved. In K-PSAQ pulping, GGM preservation was also significantly improved. At 130°C, pulp yield increase of approximately 8% in PS pulping and more than 11% in PSAQ pulping was observed. The amount of dissolved softwood hemicelluloses in black liquor was significantly increased at the higher [OH-] level and even further in the presence of PS and AQ. Simultaneously, the formation of hydroxy acids was decreased, indicating a significant stabilization of the dissolved polysaccharide fraction parallel to the pulp polysaccharides.