Scientists have made great strides toward understanding the mechanisms of speech production and perception. However, the complex relationships between the acoustic structures of speech and the resulting psychological percepts have yet to be fully and adequately explained, especially in speech produced by younger children. Thus, this study examined the acoustic structure of voiceless fricatives (/f, θ, s, ʃ/) produced by adults and typically developing children from 3 to 6 years of age in terms of multiple acoustic parameters (durations, normalized amplitude, spectral slope, and spectral moments). It was found the acoustic parameters of spectral slope and variance (commonly excluded from previous studies of child speech) were important acoustic parameters in the differentiation and classification of the voiceless fricatives, with spectral variance being the only measure to separate all four places of articulation. It was further shown that the sibilant contrast between /s/ and /ʃ/ was less distinguished in many children than adults, characterized by a dramatic change in several spectral parameters at approximately five years of age. Discriminant analysis revealed evidence that classification models based on adult data were sensitive to these spectral differences in the five-year-old age group.