The temperate evergreen needleleaf forest (ENF), primarily composed of Mongolian Scots pine (Pinus sylvestris var. mongolica), plays a pivotal role in the “The Great Green Wall” Shelterbelt Project in northern China as a major species for windbreak and sand fixation. Solar-induced chlorophyll fluorescence (SIF) has emerged as a revolutionary remote sensing signal for quantifying photosynthetic activity and gross primary production (GPP) at the ecosystem scale. Meanwhile, eddy covariance (EC) technology has been widely employed to obtain in situ GPP estimates. Although a linear relationship between SIF and GPP has been reported in various ecosystems, it is mainly derived from satellite SIF products and flux-tower GPP observations, which are often difficult to align due to mismatches in spatial and temporal resolution. In this study, we analyzed synchronous high-frequency SIF and EC-derived GPP measurements from a Mongolian Scots pine plantation during the seasonal transition (August–December). The results revealed the following. (1) The ENF acted as a net carbon sink during the observation period, with a total carbon uptake of 100.875 gC·m⁻². The diurnal dynamics of net ecosystem exchange (NEE) exhibited a “U”-shaped pattern, with peak carbon uptake occurring around midday. As the growing season progressed toward dormancy, the timing of CO₂ uptake and release gradually shifted. (2) Both GPP and SIF peaked in September and declined thereafter. A strong linear relationship between SIF and GPP (R² = 0.678) was observed, consistent across both diurnal and sub-daily scales. SIF demonstrated higher sensitivity to light and environmental changes, particularly during the autumn–winter transition. Cloudy and rainy conditions significantly affect the relationship between SIF and GPP. These findings highlight the potential of canopy SIF observations to capture seasonal photosynthesis dynamics accurately and provide a methodological foundation for regional GPP estimation using remote sensing. This work also contributes scientific insights toward achieving China’s carbon neutrality goals.