The understanding of the photochemistry of antibiotic compounds is important because it gives the direct information on the possible environmental pollution caused by them. Due to their large size, the theoretical studies of their excited-state reactions are rather challenging. In current work, we combined the on-the-fly trajectory surface-hopping dynamics, conical-intersection optimizations and excited-state pathway calculations to study the photochemistry of the trans-isomer of nitrofurantoin, a widely-used drug to treat the urinary tract infections. The dynamics-then-pathway approach was taken. First the trajectory surface hopping dynamics at the state-averaged complete-active-space self-consistent-field (SA-CASSCF) level with small active space and small basis sets were run. Second, the minimum-energy conical-intersection optimizations were performed. Finally the excited pathways from the Frank-Condon region to different reaction channels were built at the multi-state multi-reference second-order perturbation (MS-CASPT2) level with large active space and large basis set. Several possible channels responsible for the photo-induced reaction mechanism of the trans-nitrofurantoin were obtained, including the cleavage of the NO bond of the NO2 moiety, the photoisomerization at the central CN bond, and other internal conversion channels. Our findings give some preliminary explanations on available experimental observations. It is also demonstrates that the current theoretical approach is a powerful tool to explore the excited-state reactions in the photochemistry of media-sized or large-sized drug compounds.