Specimens of fossil wood preserved lignified in Pliocene brown coal and identified as Pinus armandii Francher come from an opencast coalmine at Longling in western Yunnan Province, China. Phytochemical investigation of the fossil wood isolated using liquid column chromatography seven compounds (1-7) including a new fluorene derivative named 11,11-dimethyl-11H-benzo[b]fluorene. A further 28 volatiles were detected by gas chromatography-mass spectrometry (GC-MS). Spectroscopic investigation methods, including MS and 1D and 2D-NMR techniques elucidated the structure of the seven compounds. Two types of natural products, isopimara and stilbene commonly occuring in extant and Pliocene fossil P. armandii indicate phytochemical fidelity during burial under certain circumstances in sediments. Discovery of stilbenes that can inhibit the activities of wood-destroying fungi in the Pliocene P. armandii prompts the assumption that the chemical preservation of this Pliocene fossil wood of P. armandii in brown coal might contribute to the presence of inner natural inhibitors against wood-destroying fungi.