Deprotonated para-coumaric acid is commonly considered as a model for the chromophore in photoactive yellow protein, which undergoes E → Z isomerization following absorption of blue light. Here, tandem ion mobility mass spectrometry is coupled with laser excitation to study the photochemistry of deprotonated para-coumaric acid, to show that the E isomers of the phenoxide and carboxylate forms have distinct photochemical responses with maxima in their action spectra at 430 and 360 nm, respectively. The E isomer of the phenoxide anion undergoes efficient autodetachment upon excitation of its lowest ππ* transition. For the E isomer of the carboxylate deprotomer, a one-way photoinitiated proton transfer generates the phenoxide deprotomer through a mechanism postulated to involve an excited-state enol–keto tautomerism followed by a series of ground-state rearrangements including a second proton transfer. This mechanism is supported by experiments in which the relevant intermediate keto isomer is prepared and spectroscopically probed and through master equation modeling of possible ground-state isomerization processes. The Z isomer of the carboxylate deprotomer shows a weak Z → E photoisomerization response that occurs in competition with photodestruction (presumably electron detachment), demonstrating that the E and Z isomers undergo different processes in their excited states. The study highlights the utility of isomer-selective spectroscopy for characterizing the photochemistry of isolated anions possessing multiple deprotonation sites.