Many studies have shown that during the first year of life infants start learning the prosodic, phonetic and phonotactic properties of their native language. In parallel, infants start associating sound sequences with semantic representations. However, the question of how these two processes interact remains largely unknown. The current study explores whether (and when) the relative phonotactic probability of a sound sequence in the native language has an impact on infants’ word learning. We exploit the fact that Labial-Coronal (LC) words are more frequent than Coronal-Labial (CL) words in French, and that French-learning infants prefer LC over CL sequences at 10 months of age, to explore the possibility that LC structures might be learned more easily and thus at an earlier age than CL structures. Eye movements of French-learning 14- and 16-month-olds were recorded while they watched animated cartoons in a word learning task. The experiment involved four trials testing LC sequences and four trials testing CL sequences. Our data reveal that 16-month-olds were able to learn the LC and CL words, while14-month-olds were only able to learn the LC words, which are the words with the more frequent phonotactic pattern. The present results provide evidence that infants’ knowledge of their native language phonotactic patterns influences their word learning: Words with a frequent phonotactic structure could be acquired at an earlier age than those with a lower probability. Developmental changes are discussed and integrated with previous findings.