Phytochemical investigations of the extracts from the whole plant of Gerbera piloselloides resulted in the isolation and identification of four pairs of previously unreported meroterpenoid enantiomers with coumarin- and chromone-monoterpene skeletons (1a/1b-4a/4b), including two pairs of 5-methylcoumarin monoterpenes and two pairs of 5-methylchromone monoterpenes. The structures and absolute configurations of these compounds were definitively determined through NMR and MS data, NMR calculation with DP4+ analysis, electronic circular dichroism (ECD) data, and X-ray diffraction analysis. Structurally, compounds 1-4 feature 5-methylphenylpropanoid-substituted monoterpene frameworks. All compounds were evaluated for neuroprotective activity and cytotoxicity against the human cancer cell line SGC-7901 in vitro. Compounds 1, 1a, and 1b exhibited inhibitory effects with IC