Quantum key distribution (QKD) exploits the quantum nature of light to share provably secure keys, allowing secure communication in the presence of an eavesdropper. The first QKD schemes used photons encoded in two states, such as polarization. Recently, much effort has turned to large-alphabet QKD schemes, which encode photons in high-dimensional basis states. Compared to binary-encoded QKD, large-alphabet schemes can encode more secure information per detected photon, boosting secure communication rates, and also provide increased resilience to noise and loss. High-dimensional encoding may also improve the efficiency of other quantum information processing tasks, such as performing Bell tests and implementing quantum gates. Here, we demonstrate a large-alphabet QKD protocol based on high-dimensional temporal encoding. We achieve record secret-key rates and perform the first field demonstration of large-alphabet QKD. This demonstrates a new, practical way to optimize secret-key rates and marks an important step towards transmission of high-dimensional quantum states in deployed networks.