In this study, functional near-infrared spectroscopy (fNIRS) was used to examine the brain activation patterns in the occipitotemporal cortex (OTC) associated with Chinese character recognition (CCR). Eighteen healthy participants were recruited to perform a well-designed task involving three types of stimuli including real characters, pseudo characters and checkerboards. By inspecting the brain activation difference and its relationship with behavioral data, we discovered that the left hemisphere is responsible for the orthographical information processing. Meanwhile, we found that the bilateral superior temporal gyrus (STG), bilateral Brodmann's area (BA) 19 and left fusiform gyrus were involved in high-level lexical information processing such as semantic and phonological ones, indicating that the brain activities in these regions were associated with enhanced CCR performance. In addition, by examining functional brain networks, it was discovered that increased brain connectivity in the right BA 19 exhibited significant correlation with the performance of CCR. Consequently, the combination of fNIRS technique with functional network analysis paves a new avenue for an improved understanding the cognitive mechanism underlying CCR.