Large singlet exciton diffusion lengths are a hallmark of high performance in organic based devices such as photovoltaics, chemical sensors, and photodetectors. In this study, exciton dynamics of a two-dimensional covalent organic framework, COF- 5, is investigated using ultrafast spectroscopic techniques. Following photoexcitation, the COF-5 exciton decays via three pathways: 1) excimer formation (4 ± 2 ps), 2) excimer relaxation (160 ± 40 ps), and 3) excimer decay (>3 ns). Excitation fluence-dependent transient absorption studies suggest that COF-5 has a relatively large diffusion coefficient (0.08 cm2/s). Furthermore, exciton-exciton annihilation processes are characterized as a function of COF-5 crystallite domain size in four different samples, which reveal domain- size dependent exciton diffusion kinetics. These results reveal that exciton diffusion in COF-5 is constrained by its crystalline domain size. These insights indicate the outstanding promise of delocalized excitonic processes available in 2D COFs, which motivate their continued design and implementation into optoelectronic devices.