Functional interactions in the brain are constrained by the underlying anatomical architecture, and structural and functional networks share network features such as modularity. Accordingly, age-related changes of structural connectivity (SC) may be paralleled by changes in functional connectivity (FC). We provide a detailed qualitative and quantitative characterization of the SC–FC coupling in human aging as inferred from resting-state blood oxygen-level dependent functional magnetic resonance imaging and diffusion-weighted imaging in a sample of 47 adults with an age range of 18–82. We revealed that SC and FC decrease with age across most parts of the brain and there is a distinct age-dependency of regionwise SC–FC coupling and network-level SC–FC relations. A specific pattern of SC–FC coupling predicts age more reliably than does regionwise SC or FC alone (r = 0.73, 95% CI = [0.7093, 0.8522]). Hence, our data propose that regionwise SC–FC coupling can be used to characterize brain changes in aging. Hum Brain Mapp 37:2645–2661, 2016. © 2016 Wiley Periodicals, Inc.