Herbicides such as (3,6-dichloro-2-methoxy)benzoic acid (dicamba), (4chloro-2-methylphenoxy)acetic acid (MCPA), (2,4-dichlorophenoxy)acetic acid (2,4-D), or (±)-2-(4-chloro-2-methylphenoxy)propionic acid (MCPP) are applied in the form of sodium, potassium, ammonium salts, or esters. Although esters are more biologically active, the downside is their high volatility, which is a hazard to neighboring dicotyledonous plants and spraying workers. Moreover, their commercial preparation requires the use of adjutants, which improve the wettability of the sprayed surfaces. Herbicidal ionic liquids (HILs) were introduced to overcome such drawbacks and proved to be more effective in terms of controlling weeds compared to currently applied commercial preparations. In this study, we investigated the concept of herbicidal ionic liquids that contained dicamba in a surface-active cation as an ester substituent as well as (4-chlorophenoxy)acetic acid (4-CPA), 2,4-D, MCPA, MCPP, and clopyralid as anions. The synthetized compounds were characterized in terms of surface and antimicrobial activity as well as herbicidal efficacy against garden cress (Lepidium sativum). Moreover, hydrolysis was performed using acidic, neutral, and alkaline treatments to check the conditions under which dicamba is released from the esterquat. It was revealed that the obtained HILs exhibited excellent surface properties manifested as a tendency to effectively interact with biological membranes at lower doses. This was observed as increased toxicity in comparison to reference herbicidal formulations during direct exposure; however, assessment of microbial activity in soil revealed that the ecotoxic effect was limited, most likely due to marginal mobility. Consequently, the tested HILs effectively reduced garden cress biomass production and were notably less volatile compared to commercial herbicides. Our findings present a sustainable concept of more effective usage of well-known herbicides with simultaneous reduction of the environmental burden by limiting the amount of chemicals intentionally introduced for agricultural purposes.