The hematoporphyrin derivative YHPD, a China-made product, has been clinically used in photodynamic therapy of tumors as a good photosensitizing drug. The NMR study on the structure of its major components is reported here. In terms of high performance liquid chromatography (HPLC) four major components A, B, C and D were isolated. The NMR results showed that the component A is O-acetylhematoporphyrin, B and C are two isomers of vinyldeuteroporphyrin. The spectra of 2-dimensional homonuclear correlation NMR, 2-dimensional NOE (nuclear overhauser enhancement), 13C-NMR and off-resonance as well as FAB (fast atom bombarding) mass spectrum of component D indicate that it is a protoporphyrin dimer linked by carbon-carbon bond. This finding may provide a chemical basis for understanding the difference in biological activity between YHPD and other foreign commercial HPD, as well as the composition of clinically used alkali-treated HPD and its effective component.