In this study, we investigated if children build a print-to-meaning connection via the semantic radical – a mechanism we call semantic decoding – and its interaction with phonological decoding in orthographic learning of Chinese compound characters. Ninety-two Grade 4 children were taught the pronunciations and meanings of 16 pseudocharacters and were then exposed to their written forms in short stories. Half of the characters contained semantic radicals related to the taught meaning; the other half were unrelated. Half of the children learned the pseudocharacters’ regular pronunciations; the other half learned the irregular pronunciations. There was better orthographic learning of regular than irregular pseudocharacters across measures of spelling and orthographic choice. However, the effect of semantic decoding was not as unequivocal. The findings indicate that in Chinese, decoding via phonetic radicals underpins orthographic learning. Whereas, the effect of semantic decoding might depend more on the linguistic features of the radicals and the learning environments.