Nine alkaloids and β‐sitosterol were isolated from the root of Acronychia oligophylebia Merr. (Rutaceae). Among these alkaloids, five were identified as preskimmianine (2), evolitrine (5), kokusaginine (6), skimmianine (7) and maculosidine (8). The alkaloids 2, 5 and 8 were isolated from Acronychia genus for the first time. Oligophylicidine (10) and oligophylidine (4) were new bases. Oligophyline (3) and oligophylicine (9) were first found from natural source. Based on spectroscopic data, the structures of 3, 4, 9 and 10 were postulated. The structures of 10 and 9 were confirmed by synthesis. 3 and 9 showed a wide spectrum of antifungal activity, but the actions were weak.