Ultrasound-assisted emulsification microextraction with solidification of floating organic droplet (USAEME-SFOD) has been applied to isolate hormones and other emerging contaminants from groundwater samples. Simultaneously with the extraction process, derivatization in the matrix was carried out using acetic anhydride. Quantification of studied organic pollutants was done through gas chromatography mass spectrometry (GC-MS). Hormones included β-estradiol (E2), estrone (E1), and diethylstilbestrol (DES). Other compounds belonged to groups of pharmaceuticals (diclofenac (DIC)), antiseptics (triclosan (TRC)), preservatives (propylparaben (PP) and butylparaben (BP)), sunscreen agents (benzophenone (BPH), and 3-(4-methylbenzylidene)camphor (3MBC)), repellents (N,N-diethyltoluamide (DEET)), industrial chemicals (bisphenol A (BPA), 4-t-octylphenol (4OP), 4-n-nonylphenol (4NP)). A non-toxic and inexpensive 1-undecanol was successfully used as the extraction solvent. Volume of extractant and derivatization agent, ionic strength, and time of extraction were optimized. Very low limits of detection (LoD) ranging from 0.01 to 5.9 ng/L were obtained. Recoveries ranged from 90% to 123%, with relative standard deviation being lower than 17%. The developed procedure was used to determine target compounds in groundwater collected at municipal waste landfills as well as in groundwater from wells distant from sources of pollution.