Ether groups are well-known for their unique contribution to low viscosity and high conductivity, and hence ether-functionalized ionic liquids (ILs) have been widely studied and successfully employed in various applications. However, the ether chain length effect on physicochemical properties is complex and still lacks a systematic study. In this study, an attempt was made to provide a thorough understanding for such complexities. A series of ILs functionalized with various ether groups (CmOCn-, n, m = 1, 2, or 3) were synthesized and characterized, and their properties with irregular variations along the ether chain length were recorded and systematically analyzed. Generally, the irregular variations are mediated by three interrelated factors: the C-m- tail length, the -C-n- spacer length, and hydrogen bonding interaction. For example, though ROC2- is bulkier by a CH2 unit than ROC1-, ROC2-based imidazolium ILs are less viscous and more conductive than ROC1--based analogues, since ROC1- is apt to form intermolecular rather than the five-membered-ring intramolecular hydrogen bonding with the imidazolium ring H atoms, while for ROC2- the six-membered-ring intramolecular hydrogen bonding comes into prominence.