A homologous series of Gemini surfactants, dimethylene-1,2-bis(alkyldimethyl-ammonium bromide) (referred to as n-2-n·2Br, n = 14, 16, and 18) and Fe- or lanthanide metal-based magnetic Gemini surfactants (abbreviated as n-2-n·2X, X = Fe, Ce, and Gd), were first synthesized. Measurements of surface tension and electrical conductivity determine the physical quantities related to the surface activities of n-2-n·2Br and n-2-n·2X, and the magnetic behaviors of n-2-n·2X are elucidated by superconducting quantum interference device magnetometry. Thermogravimetric analysis and differential scanning calorimetry have been used to investigate thermotropic liquid crystalline properties of all aforementioned surfactants, and the liquid crystal textures were further observed via polarizing optical microscopy. These results reveal that for magneto-responsive Gemini surfactants, both magnetic counterions and alkyl chain lengths have certain effect on surface activities, magnetism, and thermotropic phase behavior. We summed up these changes and discussed the causes, which could provide a new insight into controlling the properties of magnetic surfactants.