Alkyl β‐D‐maltosides are an important class of sugar‐based nonionic surfactants and have been widely studied. Nevertheless, it is still necessary to investigate further their amphiphilic structure‐surface property relationships. In this article, we reported a series of properties of synthetic alkyl β‐D‐maltosides (6a–6i, n = 6–18) including their hydrophilic–lipophilic balance (HLB) number, water solubility, hygroscopicity, moisture‐retention capacity, foaming ability, surface tension, thermotropic phase behavior, and skin irritation. Their HLB number and water solubility decreased with increasing alkyl chain length. Hexyl β‐D‐maltoside exhibited the strongest hygroscopicity and moisture‐retention capacity. Decyl β‐D‐maltoside and dodecyl β‐D‐maltoside possessed excellent foaming power and foaming stability. Furthermore, the critical micelle concentration (CMC) of alkyl β‐D‐maltoside (6a–6g, n = 6–14) and their surface tension at CMC decreased with increasing alkyl chain length. At last, alkyl β‐D‐maltosides (6a–6g) should be considered as safe surfactants by the skin irritation assessment. [ABSTRACT FROM AUTHOR]