In this study, two homologous series of novel herbicidal ionic liquids (HILs) were synthesized in a simple metathesis reaction between alkyl[2-(2-hydroxyethoxy)ethyl]dimethylammonium bromides and alkali metal salts of 4-chloro-2-methylphenoxyacetic acid (MCPA) or 3,6-dichloro-2-methoxybenzoic acid (dicamba), known as popular herbicides from the class of growth regulators. These HILs were subsequently mixed to prepare double-salt herbicidal ionic liquids (DSHILs). The DSHILs were characterized by substantially altered parameters of viscosity, refractive index, glass transition temperatures and surface activity compared to the average values expected for ideal mixtures of their individual components (HILs). Interestingly, DSHILs possessed superior physicochemical properties such as relatively low viscosity or facilitated formation of micelles, which emphasizes the complex nature of multi-ion interactions in the microstructures of ionic liquid mixtures. The biological tests showed improved efficiency of DSHILs against tested weeds compared to the reference herbicides and parent HILs.