The series of (Bi0.9Ho0.1)4−2x/3Ti3−xMoxO12 (BHTM) (x=0, 0.9%, 1.5%, 3.0%, and 6.0%) thin films on Pt/Ti/SiO2/Si substrates is prepared by sol-gel method, and the effect of Mo content on the microstructure and ferroelectric properties of these films are investigated. When the Mo content is not excessive, the BHTM films consisted of the single phase of Bi-layered Aurivillius phase. The B-site substitution with high-valent cation of Mo6+, in Bi3.6Ho0.4Ti3O12 films, enhanced the 2Pr (remanent polarization) and reduced the 2Ec (coercive field) of these films. The BHTM thin film with x=1.5% exhibited the best electrical properties with 2Pr of 48.4 μC/cm2, 2Ec of 263.5 kV/cm, dielectric constant of 391 (at 1 MHz), good insulting behavior, as well as the fatigue-free characteristic.