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Scientific monitoring and assessment of ecosystem services (ESs) in national parks is an important path to strengthen the management and protection of national parks. In this study, we constructed a test scheme for the ESs protection effectiveness based on the InVEST model and the Propensity score matching model (PSM). Based on this scheme, we best-matched three groups of pairs inside and outside the national park, and analyzed the magnitude and significance of differences in ESs protection between the best-matched groups by t-test, and then assessed whether the establishment of Pudacuo National Park had a protective effect on ESs. The results show that: Except for soil conservation, all ESs within Pudacuo National Park and its external 0–10 km range were higher than those in the 10–20 km area outside the national park. Moreover, the ESs within the national park and its external 0–10 km showed the same increase and decrease, and the difference between the two was small. This indicates that the existence of Pudacuo National Park effectively protects ESs and also has a positive spillover effect on its outer 0–10 km range. In addition, this study found that the soil conservation protection effect of Pudacuo National Park was slightly deficient. It exhibits weaker soil conservation than areas outside the national park. It is recommended to further strengthen the investment in soil conservation services and develop relevant measures to curb soil erosion according to local conditions.