A genuine analytical method to determine native steroids (pregnenolone, progesterone, dehydroepiandrosterone, androstenedione, testosterone, dihydrotestosterone, estrone, 17b-estradiol, and 17a-estradiol) and one anthropogenic steroid (ethynylestradiol) in environmental solid samples is presented. In summary, the sample preparation was systematically evaluated with testing different solvents and a suite of solid phase extraction materials. The optimized method utilizes the pressurized liquid extraction (PLE) technology with automated (integrated) clean-up combined with an additional off-line multi-step clean-up. The sample extracts were derivatized and analyzed utilizing a gas chromatography triple quadrupole mass spectrometry technology. This method is applicable on all types of environmental solid samples (e.g., biosolids, soils and sediments).