Extraction of structural regularity embedded in the orthography of any language is the foundation for learning to read. Recent findings from our and other laboratories have accumulated to show that such ability, as reflected in indices of statistical learning (SL), contributes to the processing and acquisition of reading a native or a foreign language. On the other hand, whether experience with specific kinds of regularity through reading behaviors modulates the corresponding ability of SL has rarely been explored. In this chapter, we report evidence from a novel SL paradigm that measures the sensitivity to temporal and spatial positional regularity. Specifically, the stimuli in the spatial positional SL (PSL) task resemble the orthographic structure of Chinese phonograms. The results showed that individual differences in the spatial PSL performance correlated with the sensitivity to orthography of Chinese characters in foreign adults. Furthermore, Chinese readers, who have extensive exposure to Chinese characters, perform better than foreigners, particularly in the spatial but not the temporal PSL task. In addition, critical components of event-related potentials underlying the sensitivity to spatial and temporal positional regularity, which are further modulated by reading experience, are identified. The behavioral and neurophysiological evidence consistently supports the functional and neuronal distinctions between spatial and temporal PSL, and the reciprocal relationship between spatial PSL and orthographic processing of Chinese characters. These findings not only extend the theoretical considerations of SL research from alphabetic to logographic orthographies, they also highlight the importance and strengths of cross-linguistic comparisons in SL and reading studies.