The detection of the pollution level of antibiotics in Daliao River system is a meaningful work. Sixteen antibiotics (6 sulfonamides, 5 fluoroquinolones, 3 tetracyclines and 2 chloramphenicols) were simultaneously quantified with solid-phase extraction (SPE) and liquid chromatography-tandem mass spectrometry (LC-MS/MS). In the SPE procedure, methanol and 2% (v/v) ammonia/methanol were used as the elution solvents in sequence to reduce the elution volume and improve the recovery. The results showed that this method have good sensitivity and enrichment effect for the target antibiotics in aqueous water, the recoveries ranged from 69.5% to 122.6%, the detection limits ranged from 0.05 ng/L to 0.32 ng/L. Thirteen antibiotics were found in the river water of Daliao River water system. Sulfa antibiotics were widely distributed, in which sulfamethoxazole was detected in all the sampling sites. The concentration of fluoroquinolones was relatively high in some sampling sites. The highest detection concentration of enoxacin was 41.3 ng/L. The frequencies and concentrations of tetracyclines and chloramphenicols were lower. In the upper reaches of the river, the concentrations of the 4 types ofantibiotics appeared lower, but around the large cities such as Shenyang City, Benxi City, Liaoyang City, the concentrations showed higher levels. The study indicated that the Daliao River water system suffered from the pollution of antibiotics to a certain extent.