A typical piezoelectric energy harvester is a bimorph cantilever with two layers of piezoelectric material on both sides of a flexible substrate. Piezoelectric layers of lead-based materials, typically lead zirconate titanate, have been mainly used due to their outstanding piezoelectric properties. However, due to lead toxicity and environmental problems, there is a need to replace them with environmentally benign materials. Here, our main efforts were focused on the preparation of hafnium-doped barium titanate (BaHfxTi1−xO3; BHT) sol–gel materials. The original process developed makes it possible to obtain a highly concentrated sol without strong organic complexing agents. Sol aging and concentration can be controlled to obtain a time-stable sol for a few months at room temperature, with desired viscosity and colloidal sizes. Densified bulk materials obtained from this optimized sol are compared with a solid-state synthesis, and both show good electromechanical properties: their thickness coupling factor values are around 53% and 47%, respectively, and their converse piezoelectric coefficient values are around 420 and 330 pm/V, respectively. According to the electromechanical properties, the theoretical behavior in a bimorph configuration can be simulated to predict the resonance and anti-resonance frequencies and the corresponding output power values to help to design the final device. In the present case, the bimorph configuration based on BHT sol–gel material is designed to harvest ambient vibrations at low frequency (<200 Hz). It gives a maximum normalized volumetric power density of 0.03 µW/mm3/Hz/g2 at 154 Hz under an acceleration of 0.05 m/s2.