This study aimed to determine how Chinese children adapt to Chinese orthography–phonology correspondence by acquiring phonetic radical awareness (PRA). This study used two important Chinese encoding approaches (rote and orthographic approaches) as the developmental trajectory, in which the present study hypothesized that phonological awareness (PA) exerts not only a direct influence on PRA but also an indirect influence through paired– associate learning (PAL). We also explored whether the association between PA and PAL is affected by the complexity of visual stimuli embedded in PAL. This study recruited 70 s-grade students to participate in various tests, which assessed (a) PA (measured by onset and rhyme awareness), (b) PRA (measured by regularity and consistency of phonetic radicals), (c) PAL (measured by learning performance on strokes; pattern-object and strokes pattern-syllable mapping), and (d) Chinese character recognition ability. Path analyses indicated that (1) character size had a significant positive correlation with PRA but not with PAL, (2) PAL fully mediated the association between PA and PRA, and (3) compared with PAL with a low stroke count, PA had a stronger relationship with PAL with a high stroke count. The results of this study were consistent with previous studies and suggest that PRA is the most important literacy skill for children in the middle of their learning-to-read stage. The results also augment existing literature by revealing that PRA acquisition is increased by PAL supported by PA, rather than by PA alone. Moreover, when the visual complexity of PAL increases, the support of PA to PAL would increase to make up for the working memory shortage.