We fabricated the crosslinked films using p-hexadecoxyphenol (p-HP), which is amphiphilic and can form polyion complexes with formaldehyde at the air-water interface. The behavior of polyion complexation at the air-water interface and the surface structure of LB films was investigated by Brewster angle microscope(BAM) and scanning Maxwell-stress microscope (SMM), respectively. Also, the electrical properties for crosslinking in phenol-formaldehyde LB films were investigated by measuring conductivity and dielectric constant. The conductivities of p-HP LB films are as follows: heat-treatment of 1% formaldehyde subphase(3.76$ imes$10$^{-15}$ ~4.76$ imes$10$^{-1}$5[S/cm])<pure water (1.33$ imes$10$^{-14}$ ~1.74$ imes$10$^{-14}$ [S/cm]). Also, relative dielectric constants of p-HP LB films were reduced from 6.76~7.84 (pure water) to 2.97~3.25 (heat-treatment of 1% formaldehyde subphase))