Unsaturated natural and synthetic phosphatidyl cholines (PCs), when treated with tannic acid and OsO4, demonstrated a substantial increase in contrast as compared to PC treated only with OsO4. This was not observed when phosphatidyl ethanolamine (PEA) was similarly exposed to tannic acid. The increased electron density observed in the lamellar organization of the PC phospholipids was limited to the hydrophilic layers corresponding to the polar regions of the phospholipid molecules. The repeating periods of lamellae were identical in PC, treated with both tannic acid and OsO4, and when treated only with OsO4. In each case, this approximated 45 A. The enhancement of membrane contrast by tannic acid in the presence of OsO4 is interpreted as being at least in part due to its multivalent capacity, binding to reactive sites on choline, as well as with OsO4.