Two new porphycenes functionalized with ferrocenyl pendants have been synthesized and characterized spectroscopically and structurally. The porphycene-based emission in porphycene ferrocene dyads was switched on and off by the reversible control of the ferrocenyl pendant redox states. Transient absorption spectroscopy with a femtosecond laser-pulsed technique has successfully detected the picosecond charge-separated excited state of the dyad upon Q-band excitation of the porphycene ring.