Self‐assembled donor/acceptor dyads are of current interest as they are biomimetic to the natural photosynthetic conversion system. Herein, we present an ultrahigh‐vacuum scanning tunneling microscopy and scanning tunneling spectroscopy (UHV‐STM/STS) study of ex situ self‐assembled supramolecular dyads consisting of fulleropyrrolidines (PyC2C60) axially ligated to zinc(II) tetraphenylporphyrin (ZnTPP), self organized on a 4‐aminothiophenol (4‐ATP) self‐assembled monolayer on gold(111). These dyads show both bias‐polarity‐dependent apparent height in STM images and highly rectifying behavior in tunneling spectroscopy. First‐principles density functional theory calculations clarify the conformational and electronic properties of the 4‐ATP/ZnTPP/PyC2C60 system. Interestingly, we find easier tunneling for electrons moving from the acceptor side of the dyads to the donor side, in the inverse …