The lignification process from sapwood (sW) to heartwood (hW) in ray parenchyma cells (P ray ) of Pinus densiflora has been analyzed by means of ultraviolet (UV) microscopy, acetyl bromide (CH 3 COBr) lignin determination, and time-of-flight secondary ion mass spectrometry (TOF-SIMS). The cell wall layers were localized by polarized optical microscopy (POM). POM revealed that P ray have almost no secondary wall in sW and have only the outer layer of secondary wall (S 1 ) in the transition zone (TZ) and hW. UV microscopic observations indicated that the secondary wall of P ray , which is in contact with ray tracheids (Tr ray ), begins to lignify in sW, while the secondary wall of P ray , which is not in contact with Tr ray , is partially lignified in the TZ. The secondary wall of both types of P ray is completely lignified in hW. The CH 3 COBr lignin content in sW is slightly lower than that in hW. In the TOF-SIMS measurements, the relative intensities of the secondary ions of guaiacyl-lignin (G-lignin) in the rays in sW are significantly lower than those in hW.