A series of polyethylene glycol‐linked Gemini fatty alcohol phosphate surfactants (GFAP) were prepared with long chain n‐alkanol (C = 8, 12, 16, 18), polyethylene glycol (PEG‐200, PEG‐400, PEG‐600, PEG‐800, PEG‐1000) and phosphorus oxychloride (POCl3). The structure of the prepared surfactants was characterized by Fourier transform infrared spectrometer (FT‐IR). The surfactants were employed for the modification of chrome‐tanned leather. The morphological changes of chrome‐tanned leather and modified chrome‐tanned leather were observed by scanning electron microscopy (SEM). The relationship between the alkyl chain length and molecular weight of the PEG and the hydrophobicity, softness, mechanical strength of modified chrome‐tanned leather was also discussed. The experimental results showed that the mechanical strength and softness of modified chrome‐tanned leather were enhanced with an increase of alkyl chain length, while the hydrophobicity, mechanical strength and softness were decreased with an increase of molecular weight of the PEG. The hydrophobicity, mechanical strength and softness of modified chrome‐tanned leather were optimized for an alkyl chain length of 16. Therefore, 16–200 Gemini phosphate surfactants with an alkyl chain length of 16 and a PEG molecular weight of 200 have a good comprehensive modification effect on Chrome‐tanned leather, the tensile strength, tear strength and softness of modified chrome‐tanned leather are 57.07 N mm−2, 79.49 N mm−1, 9.73 mm, respectively.