[eng] In this work, low-force stereolithography (SL) was exploited for 3D printing and prototyping bespoke fluidic devices for accommodating nonsupported microelectromembrane extraction (μEME). The analytical performance of 3D-printed μEME devices with distinct cross-sections, including square, circle, and obround, and various channel dimensions was explored against that of commonly used circular polytetrafluoroethylene (PTFE) tubing in flow injection systems. A computer-controlled millifluidic system was harnessed for the (i) automatic liquid-handling of minute volumes of donor, acceptor, and organic phases at the low μL level that spanned from 3 to 44 μL in this work, (ii) formation of three-phase μEME, (iii) in-line extraction, (iv) flow-through optical detection of the acceptor phase, and (v) solvent removal and regeneration of the μEME device and fluidic lines. Using methylene blue (MB) as a model analyte, experimental results evinced that the 3D-printed channels with an obround cross-section (2.5 mm × 2.5 mm) were the most efficient in terms of absolute extraction recovery (59%), as compared to PTFE tubing of 2.5 mm inner diameter (27%). This is attributed to the distinctive convex interface of the organic phase (1-octanol), with a more pronounced laminar pattern, in 3D-printed SL methacrylate-based fluidic channels against that of PTFE tubing on account of the enhanced 1-octanol wettability and lower contact angles for the 3D-printed devices. The devices with obround channels were leveraged for the automatic μEME and in-line clean-up of MB in high matrix textile dyeing wastewater samples with relative recoveries ≥81%, RSD% ≤ 17.1% and LOD of 1.3 mg L−1. The 3D-printed nonsupported μEME device was proven superb for the analysis of wastewater samples with an elevated ionic strength (0.7 mol L−1 NaCl, 5000 mg L−1 Na2CO3, and 0.013 mol L−1 NaOH) with recorded electric currents below 12 μA.