Quantum chemical methods and time-resolved laser spectroscopy are employed to elucidate ultrafast charge-separation processes in triphenylamine (TPA) derivatives upon photoexcitation. When changing the ambient solvent from non-electron-accepting to electron-acceptor solvents, such as chloroform, a vastly extended and multifaceted photochemistry of TPA derivatives is observed. Following initial excitation, two concurrent charge-transfer processes are identified. When the TPA derivative and solvent molecules are arranged in a configuration that favors efficient electron transfer, charge separation occurs immediately, leading to the formation of a radical cation of the TPA derivative. This highly reactive species can subsequently combine with other TPA derivative molecules to yield a dimeric species. Alternatively, if the molecular positioning upon photoexcitation is not optimal, relaxation back to the S