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A simultaneous liquid-phase microextraction method was investigated as an alternative to the traditional dispersive liquid–liquid microextraction for the determination of copper. The potential of this approach is based on the simultaneous complexation and extraction process (SCE) using an innovative spraying apparatus forming finer droplets. Method optimization was performed after ensuring the complexation of copper with a novel ligand, namely 8-(1,3-dihydroxy-1-phenylpropan-2-ylimino)methyl)-7-hydroxy-4-phenyl-2H-chromen-2-one ligand with respect to the conventional FAAS system; the detection power of the new developed system (spraying-assisted fine droplet formation-based simultaneous liquid-phase microextraction-slotted quartz tube-flame atomic absorption spectrometry, SAFDF-SLPME-SQT-FAAS) was about 33.8. The quantification and detection values were calculated to be 8.7 and 2.6 µg L−1. Recovery studies were tested in clove extract samples. Obtained percent recoveries were between 96.0 and 103.3% highlighting the applicability and the accuracy of the developed method.