Thin films of Bi4-xSmxTi3O12(0$leq$x$leq$2) were prepared on Pt/Ti/SiO2/Si(100) at $700^{circ}C$ using spin-coating with sols derived from Bi-Sm-Ti complex alkoxides. From X-ray diffraction analysis, it was observed that Sm-substituted phases resembled ferroelectric Bi4Ti3O12 in structure. Variations of their lattice parameters depending on the amount of Sm-substitution showed that an anomalous structural distortion might exist at x=1. The grain sizes of the thin films decreased from 0.115 ${mu}{ extrm}{m}$ to 0.078${mu}{ extrm}{m}$ with increasing the amount of Sm-substitution. The dielectric constants and the remanent polarizations of the thin films decreased with increasing the amount of the Sm-substitution, which were related to decrease of the stereo-active Bi3+ ion contributing to polarization. However, these values were exceptionally high at x=1, compared to those of the other substituted phases. Such an anomaly suggests that the phase of x=1 has 1:1 chemical ordering between Sm and Bi in structure. The thin films of all compositions except x=2 showed ferroelectricity. The thin film of x=2 was paraelectric, whose grains were too fine to exhibit ferroelectricity.