The  bond length in peroxides is about 1.45 Å, and the  angles (R = H, C) are about 110° (water-like). Characteristically, the  dihedral angles are about 120°. The  bond is relatively weak, with a bond dissociation energy of , less than half the strengths of , , and  bonds.
Hydroperoxides are typically more volatile than the corresponding alcohols:
* tert-BuOOH (b.p. 36°C) vs tert-BuOH (b.p. 82-83°C)
* Methyl hydroperoxide| (b.p. 46°C) vs Methanol| (b.p. 65°C)
* cumene hydroperoxide (b.p. 153°C) vs cumyl alcohol (b.p. 202°C)