Double hydrogen transfer occurring in both ground and the lowest electronically excited singlet states was studied for a series of 19 differently substituted porphycenes. The rates of tautomerization have been determined using femtosecond pumpprobe spectroscopy with polarized light. The values vary by over 3 orders of magnitude, suggesting the importance of tunneling. Good correlation exists between the values of the rates and the parameters characterizing the strength of two intramolecular hydrogen bonds: proton NMR shift, distance between the hydrogen-bonded nitrogen atoms, and the NH stretching frequency. While hydrogen-bond strength is the main factor determining the rate of double hydrogen transfer, other factors, such as static and dynamic symmetry breaking and the population of low-frequency vibrations also have to be taken into account.