Natural gas hydrate has been a critical risk to the safety of offshore oil and gas well test and subsea transportation. Herein, the effect of three quaternary ammonium salt (QAS) surfactants with monoethylene glycol (MEG) to methane hydrate agglomeration in water-oil system was experimentally studied by a rocking cell. Based on the hydrate volume fraction and the slider trajectory, a classification method of the gas hydrate anti-agglomerants was established. All the QASs in this work show the capability of reducing hydrate agglomeration, among which N1,N3-didodecyl-N1,N1,N3,N3-tetramethylpropane-1,3-diaminium chloride (AA-2) has the best anti-agglomerating performance, and the slider moved at a large trajectory of 61-174 mm. The three QASs were compounded with 5, 10, and 15 wt% (based on water) MEG, respectively. Experimental results showed that AA-2 compounded with MEG (10 wt%) can effectively prevent hydrate agglomeration. The slider moved in the cell at the full trajectory range, showing the compound of grade A performance. The compound of QAS and MEG shows a synergistic effect. The addition of QAS can significantly reduce the required MEG dosage for the hydrate blockage prevention than the MEG only situation. Considering the economic factors of the filed hydrate management, the combination application of QAS + MEG may provide a promising option.