Our recent work showed there existed a composition window for mixed Langmuir monolayers of homopolystyrene (h-PS) and a symmetric diblock copolymer polystyrene-block-poly(2-vinylpyridine) (PSb-P2VP) to form neck I ace-network structures at the air/water interface. In order to Study further the possible mechanism and control the network Structure (i.e., surface coverage and nanoaggregate diameter), effects of spreading Solution concentration and volume, subphase temperature, and transfer pressure oil the network structure were studied by the Langmuir monolayer technique and tapping mode atomic force microscopy. With the increase of transfer pressure, there existed a novel nonlinear behavior for the nanoaggregate diameter first to increase, theen to decrease, and finally to increase again, While the Surface coverage tended to increase step by step. Moreover, with the elevation of temperature, chain motion between the adjoining nanoaggregates tended to be improved and thus the nanoaggregate diameter tended to be more uniform.