Infrared spectroscopy was used to monitor and characterize solutions used in the preparation of PZT 53/47 powders, dried gels, and thin layers deposited on platinized silicon substrates. It was found that careful control of the chemistry of the precursor solutions, in particular the control of the formation of esters and their elimination, resulted in reproducible solutions which could be used to prepare thin layers with superior properties. In addition, it was found that phase development and microstructure were related to the precursor chemistry. Single‐phase perovskite layers with uniform microstructures resulted from ester‐free solutions and were suitable for ferroelectric applications (Pr∼ 22 μC/cm2,Ec∼ 80 kV/cm,K∼ 800, ta