A novel absorbing pervaporation hybrid technique has been evaluated experimentally for the recovery of ammonia from the gas mixture in a recycle loop of synthesis plants. This process of hybridization brings together the combination of energy-efficient membrane gas separation based on poly(dimethylsiloxane) poly(diphenylsilsesquioxane) with a high selective sorption technique where a water solution with polyethylene glycol 400 (PEG-400) was used as the liquid absorbent. Process efficiency was studied using the pure and mixed gases. The influence of PEG-400 content in aqueous solutions on process selectivity and separation efficiency was studied. The ammonia recovery efficiency evaluation of an absorbing pervaporation technique was performed and compared with the conventional membrane gas separation. It was shown that the absorbing pervaporation technique outperforms the conventional membrane method in the whole range of productivity, producing the ammonia with a purity of 99.93 vol.% using the PEG 80 wt.% solution. The proposed method may be considered as an attractive solution in the optimization of the Haber process.