The present study is focused on the processing of columnar lead zirconate titanate (PZT) structures on Ti/Pt-coated silicon substrates using electrohydrodynamic deposition. It was found that the as-deposited PZT structure is highly dependent on the concentration of the sprayed precursor, which is believed to be the characteristic of electrohydrodynamic deposition. 0.01, 0.03, 0.06, 0.12, 0.3 and 0.6M PZT sols were used to prepare as-deposited structures. Columnar PZT structures, which are important for the processing of 1-3 composites, were obtained with the 0.6M sol. As-deposited and heat-treated columnar PZT structures were investigated using scanning electron microscopy and X-ray diffraction. The development of the PZT columns was studied by observing the cross-section of the structures deposited over different time sprays, revealing a three-stage growth process for these structures. The affect of substrate temperature on the columnar structure was also analysed by studying the density of the columns. Finally, a 1-3 composite was produced by infiltrating photoresists into the columnar PZT structures and the relative permittivity and dissipation factor of such composite were measured as 105 and 0.021. Modelling the structures as a PZT and a polymer capacitor connected in parallel in the PZT/polymer composite suggests that the relative permittivity of PZT columnar material is approximately 154.