Two novel resveratrol dimers, vaticanols O (1) and P (2), were isolated from the bark and stem wood of Vatica albiramis (Dipterocarpaceae), a genus rich in highly oligomerized stilbenoids. Along with seven known constituents, their structures were elucidated by comprehensive spectroscopic analyses, including 1D and 2D NMR, HR-ESI-MS, and ECD measurements. Compound 1 possesses a rare fused ring skeleton comprising a 1,2-dihydrobenzo[1, 2-b:4,3-b'] difuran unit, while 2 features a 6,10b-dihydro-1H-anthra[1, 9-bc] furan skeleton with an additional C1 unit. Absolute configurations were assigned from NOESY correlations and electronic circular dichroism (ECD) data, supported by molecular modeling. Importantly, both dimers can be generated from ( -)-(E)-ε-viniferin under UV irradiation, as verified by LC-ESI-QTOF-MS, providing experimental support for plausible non-enzymatic biosynthetic pathways. These UV-induced transformations, monitored by LC-ESI-QTOF-MS, represent the first report of photo-triggered structural diversification of ( -)-(E)-ε-viniferin.