The structural and electrical properties of amorphous BaSm2Ti4O12 (BSmT) films on a TiN/SiO2/Si substrate deposited using a RF magnetron sputtering method were investigated. The deposition of BSmT films was carried out at 300˚C in a mixed oxygen and argon (O2 : Ar = 1 : 4) atmosphere with a total pressure of 8.0 mTorr. In particular, a 45 nm-thick amorphous BSmT film exhibited a high capacitance density and low dissipation factor of 7.60 fF/μm2 and 1.3%, respectively, with a dielectric constant of 38 at 100 kHz. Its capacitance showed very little change, even in GHz ranges from 1.0 GHz to 6.0 GHz. The quality factor of the BSmT film was as high as 67 at 6 GHz. The leakage current density of the BSmT film was also very low, at approximately 5.11 nA/cm2 at 2 V; its conduction mechanism was explained by the the Poole-Frenkel emission. The quadratic voltage coefficient of capacitance of the BSmT film was approximately 698 ppm/V2, which is higher than the required value (<100 ppm/V2) for RF application. This could be reduced by improving the process condition. The temperature coefficient of capacitance of the film was low at nearly 296 ppm/˚C at 100 kHz. Therefore, amorphous BSmT grown on a TiN substrate is a viable candidate material for a metal-insulator-metal capacitor.