A new amphiphile: octyl-β-D-glucopyranoside along with a single-source precursor, barium titanium methoxyethoxide, were used to develop a facile route for synthesis of BaTiO3, via either a hydrolytic or a nonhydrolytic method. The average particle size for the samples was on the order of 20 to 30 nm, while that for the control samples (without the amphiphile) ranged from 100 nm to several microns. The high-resolution transmission electron microscopy (HRTEM) images and selected-area electron- diffraction patterns revealed that these nanoparticles were single crystalline; the Raman active longitudinal optical modes observed in calcined (650 °C) samples at 718 and 304 cm−1 directly indicated the presence of tetragonal domains in an overall cubic lattice structure. Moreover, the one-step nonhydrolytic approach developed for the synthesis of BaTiO3 is fast, and it eliminates tedious steps such as prolonged refluxing and aging. Thermogravimetric and Fourier transform infrared (FTIR) analysis were performed to investigate the role of octyl-β-D-glucopyranoside in the evolution of the perovskite phase, grain size, and morphology. These techniques suggested that van der Waals type of interactions were present between the amphiphile and barium titanium methoxyethoxide oligomers, and in turn they led to the controlled growth of nanoparticles.