Conjugated molecules bearing carbonyl groups typically exhibit weak fluorescence emission due to the presence of a non-radiative n-π∗ transition state. Strong fluorescence emission from n-π∗ chromophores has been sought through the use of synthetic approaches that incorporate strong electron donors, such as amines, into the conjugated structures. As an alternative to these existing approaches, we investigated two charge-transfer strategies using a series of 1-benzopyran-2-one (coumarin) derivatives. The first strategy involved attaching chromophoric aryl moieties at the 7 position of coumarin. This molecular control produced two effects: the n-π∗ transition state was destabilized and an intramolecular charge-transfer (ICT) state was generated. The photoluminescence quantum yields (PLQYs) of the bichromophoric dyads increased with the π-conjugation length of the aryl groups, and a PLQY as high as 0.80 was achieved. The second strategy facilitated exciplex fluorescence in poly(N-vinylcarbazole) (PVK) films within which coumarin derivatives have been molecularly dispersed. A thermodynamic analysis based on electrochemical data indicated that exciplex generation involved electron transfer from PVK to photoexcited coumarin molecules. Exciplex fluorescence was uniquely advantageous in its ability to tune the fluorescence emission color upon addition of electron donors having oxidation potentials less positive than that of PVK. Mechanistic studies, including femtosecond laser flash photolysis, were conducted to identify the molecular parameters that governed the two fluorescence properties. A mechanistic understanding may provide useful insights into the development of electrofluorescent materials that harness triplet as well as singlet excitons.