A recipe has been elaborated for preparing barium titanate (BaTiO3) particles in a nucleation route which is mediated by thermal decomposition of polymeric barium titanium methacrylate. Adjustment of particle size d in the range from 10 nm to 1.5 mu m is easily done by choosing appropriate reaction temperatures and tempering atmospheres. In particular, doping with paramagnetic probe ions such as Mn2+, Gd3+ or Cr3+ can be readily accomplished by just adding the corresponding metal acetates to the monomeric precursor. In addition to well approved standard techniques such as scanning electron microscopy (SEM), X-ray diffraction (XRD) and differential scanning calorimetry (DSC), the complementary spectroscopic methods electron paramagnetic resonance (EPR), nuclear magnetic resonance (NMR), X-ray absorption near edge structure (XANES) and FT-Raman are applied to characterise the micro- and nanocrystalline BaTiO3 powders prepared and to study the phase transition behaviour in dependence on the mean particle size. In contrast to expectation from literature, the dimensionality effect does not manifest itself in a temperature shift of the ferroelectric phase transition but, instead, the tetragonal-to-cubic phase transition is smeared out at reduced particle size and an increasing tetragonal-to-cubic phase admixture is detected.