Galeola nudifolia is a medicinal orchid recognized as a valuable source of structurally diverse natural products with potential therapeutic applications. Its chemical composition and biological activities remain largely unexplored, particularly with respect to anti-neuroinflammatory activity. Bioassay-guided investigation of G. nudifolia fruits led to the isolation of six new compounds, including three benzylresorcinol (1–3) and three benzylstilbene (4–6) derivatives, together with seven known compounds (7–13). Their structures were elucidated through comprehensive spectroscopic analyses. The anti-neuroinflammatory activities were evaluated in LPS-stimulated BV-2 microglial cells by measuring NO production. Most of compounds exhibited significant inhibitory effects on NO production with IC₅₀ values ranging from 6.59 to 15.79 μM. Notably, compounds 6 (IC₅₀ = 7.77 μM), 10 (IC₅₀ = 7.48 μM), 11 (IC₅₀ = 8.62 μM), and 12 (IC₅₀ = 6.59 μM) showed superior inhibitory potencies compared to the positive control (grossamide, IC₅₀ = 9.23 μM). Immunofluorescence analyses showed that compound 12 reduced iNOS expression and NF-κB p65 nuclear translocation, whereas molecular docking provided qualitative predictions of possible interactions of compounds 6 and 10–12 with iNOS and the IκBα/NF-κB complex. These findings expand the chemical diversity of G. nudifolia and identify its benzylstilbene derivatives as natural products with anti-neuroinflammatory activity.