Recent advances have enabled studies of atom-ion chemistry at unprecedentedly low temperatures, allowing precision observation of chemical reactions and novel chemical dynamics. So far, these studies have primarily involved reactions between atoms and atomic ions or non-polar molecular ions, often in their electronic ground state. Here, we extend this work by studying an excited atom-polar-molecular-ion chemical reaction (Ca* + BaCl+) at low temperature in a hybrid atom-ion trapping system. The reaction rate and product branching fractions are measured and compared to model calculations as a function of both atomic quantum state and collision energy. At the lowest collision energy we find that the chemical dynamics differ dramatically from capture theory predictions and are primarily dictated by the radiative lifetime of the atomic quantum state instead of the underlying excited-state interaction potential. This reaction blockading effect, which greatly suppresses the reactivity of short-lived excited states, provides a means for directly probing the reaction range and also naturally suppresses unwanted chemical reactions in hybrid trapping experiments.