Temporal information is essential for effective perception and action in the dynamic environment in which we exist. However, our ability to use information about time intervals flexibly to direct attention to an expected point in time has until recently been unexplored. Here we report a series of behavioural, neuroimaging and electrophysiological experiments that investigate and define the ability to orient attention in the temporal domain. These studies reveal that we are able to orient attention selectively to different time intervals, enhancing behavioural performance. These effects are mediated by a left-hemisphere dominant frontal-parietal system, which partially overlaps with the networks involved in spatial orienting. The optimisation of behaviour by temporal orienting appears to be achieved via motor-related mechanisms, in contrast to the typical perceptual enhancements produced by spatial attention. From a more general perspective, these findings illustrate the flexibility of attentional functions in the human brain.