The spectroscopic and dynamic properties of methyl ferulate -a naturally occurring ultraviolet-protecting filter-and microsolvated methyl ferulate have been studied under molecular beam conditions using resonance enhanced multiphoton ionization spectroscopy in combination with quantum chemical calculations. We demonstrate and rationalize how the phenyl substitution pattern affects the state ordering of the lower excited singlet state manifold and what the underlying reason is for the conformationdependent Franck-Condon (FC) activity in the UV-excitation spectra. Studies on microsolvated methyl ferulate reveal potential coordination sites and the influence of such a coordination on spectroscopic properties. Our quantum chemical studies also enable us to obtain a quantitative understanding of the dominant excited-state decay routes of the photoexcited ππ * state involving a ∼3 ns intersystem crossing pathway to the triplet manifold -which is much slower than found for coumarates-and a relatively fast intersystem crossing back to the ground state (∼30 ns). We show that a common T 1 /S 0 crossing can very well explain the observation that T 1 lifetimes are quasi independent of the phenyl substitution pattern.