Cuticular hydrocarbons (CHCs) are diverse in insects, and include variable classes of cuticular lipids, contributing to waterproofing for insects under desiccation environments. However, this waterproofing function of CHCs is still not well characterized in aphids. In this study, we compared CHC profiles for desiccation-resistant and nonresistant genotypes of the grain aphid, Sitobion avenae (Fabricius), in responses to desiccation. Our result showed that a total of 27 CHCs were detected in S. avenae, and linear alkanes (e.g., n-C29) were found to be the predominant components. Long-chain monomethyl alkanes were found to associate closely with water loss rates in S. avenae in most cases. Resistant genotypes of both wing morphs had higher contents of short-chain n-alkanes under control than nonresistant genotypes, showing the importance of short-chain n-alkanes in constitutive desiccation resistance. Among these, n-C25 might provide a CHC signature to distinguish between desiccation-resistant and nonresistant individuals. Compared with linear alkanes, methyl-branched CHCs appeared to display higher plasticity in rapid responses to desiccation, especially for 2-MeC26, implying that methyl-branched CHCs could be more sensitive to desiccation, and play more important roles in induced desiccation-resistance. Thus, both constitutive and induced CHCs (linear or methyl-branched) can contribute to adaptive responses of S. avenae populations under desiccation environments. Our results provide substantial evidence for adaptive changes of desiccation resistance and associated CHCs in S. avenae, and have significant implications for aphid evolution and management in the context of global climate change.