Ferroelectric PZT 53:47 thin films were prepared by two different solution deposition methodologies. Both routes utilized carboxylate and alkoxide precursors and acetic acid, which served as both a solvent and a chemical modifier. We have studied the effects of solution preparation conditions on film microstructure and ferroelectric properties, and have used NMR spectroscopy to characterize chemical differences between the two precursor solutions. Films prepared by a sequential precursor addition (SPA) process were characterized by slightly lossy hysteresis loops, with a Pr of 18.7 μC/cm2 and an Ec of 55.2 kV/cm. Films prepared by an inverted mixing order (IMO) process were characterized by well saturated hysteresis loops, a Pr of 26.2 μC/cm2 and an Ec of 43.3 kV/cm. While NMR investigations indicated that the chemical environments of both the proton and carbon species were similar for the two processes, differences in the amounts of by-products (esters, and therefore, water) formed were noted. These differences apparently impacted ceramic microstructure. Although both films were characterized by a columnar growth morphology, the SPA derived film displayed a residual pyrochlore layer at the film surface, which did not transform into the stable perovskite phase. The presence of this layer resulted in poor dielectric properties and lossy ferroelectric behavior.