The majority of tea studies have relied on neuropsychological measures, and much fewer on neuroimaging measures, especially for interregional connections. To date, there has been no exploration of the effect of tea on system-level brain networks. We recruited healthy older participants to two groups according to their history of tea drinking frequency and investigated both functional and structural networks to reveal the role of tea drinking on brain organization. The results showed that tea drinking gave rise to the more efficient structural organization, but had no significant beneficial effect on the global functional organization. The suppression of hemispheric asymmetry in the structural connectivity network was observed as a result of tea drinking. We did not observe any significant effects of tea drinking on the hemispheric asymmetry of the functional connectivity network. In addition, functional connectivity strength within the default mode network (DMN) was greater for the tea-drinking group, and coexistence of increasing and decreasing connective strengths was observed in the structural connectivity of the DMN. Our study offers the first evidence of the positive contribution of tea drinking to brain structure and suggests a protective effect on age-related decline in brain organisation.