Polystyrene microfibers containing lower-rim substituted calix[4]arene with phosphinoyl pendant arms were easily prepared in one-step procedure by electrospinning. A specific feature of the fibers is the difference in their functionality at the surface and in the bulk. The graded structure of the fibers was shown by analyses. The calix[4]arene concentration in the 3-5 nm surface layer was 50% higher than the theoretically calculated if calix[4]arene was uniformly distributed in the fibers. A six-coordinated complex was between the calix[4]arene included in the fibers and Ni2+ ions. The distribution of phosphorus along the fibers is uniform, as evidenced by X-ray mapping.