Writing is an essential tool for human communication and involves multiple linguistic, cognitive, and motor processes. Chinese, a logographic writing system, differs remarkably from the writing systems of alphabetic languages. The neural substrates of Chinese writing are largely unknown. Using functionalmagnetic resonance imaging (fMRI) in a copying task, this study probed the neural underpinnings of orthographic access during Mandarin Chinese writing by employing the word-frequency effect. The results showed that writing low-frequency characters evoked greater activation in the bilateral superior/middle/inferior frontal gyrus, superior/inferior parietal lobule, and fusiform gyrus than writing high-frequency characters. Moreover, psychophysiological interaction (PPI) analysis demonstrated that the word-frequency effect modulated functional connectivity within the frontal-occipital networks and the parietal-occipital networks. Together, these findings illustrate the neural correlates of orthographic access for Mandarin Chinese writing, shedding new light on the cognitive architecture of writing across various writing systems.