Green analytical chemistry aims at developing analytical methods with minimum use and generation of hazardous substances for the protection of human health and the environment. To address this need, a green analytical protocol has been developed for the analysis of anionic compounds integrating electromembrane extraction (EME), dual-channel nanoelectrospray ionization (nanoESI), and a miniature mass spectrometer. Haloacetic acids (HAAs) have attracted considerable public concern due to their adverse effects on human health and were selected as model analytes for method development. A flat membrane EME device was developed and assembled in-house. Optimization of fundamental operational parameters was performed using single-factor test and response surface methodology. Both the EME acceptor phase and an imidazolium-based dicationic ionic liquid (DIL), 1,1-bis(3-methylimidazolium-1-yl) butylene difluoride (C4(MIM)2F2), were subjected to dual-channel nanoESI and miniature mass spectrometry analysis based on a charge inversion strategy, where positively charged complexes were formed. Enhancement in signal intensity by as much as 2 magnitudes was achieved in the positive-ion mode compared to the negative-ion mode in the absence of the dicationic ion-pairing agent. The developed protocol was validated, obtaining good recoveries ranging from 82.7 to 109.9% and satisfactory sensitivity with limits of detection (LODs) and quantitation (LOQs) in the ranges of 1-5 and 2-10 μg/L, respectively. The greenness of the analytical procedure was assessed with a calculated score of 0.71, indicating a high degree of greenness. The developed method was applied to the analysis of real environmental or municipal water samples (n = 16), exhibiting appealing potential for outside-the-laboratory applications.