Aliovalent Nb doping (less than or equal to 10 at.%) of sol-gel-derived lead zirconate titanate (PZT) thin films was investigated with the intention of improving the ferroelectric properties. Nb addition was found to significantly alter the perovskite crystallization by stabilizing the transient pyrochlore phase, resulting in the retention of pyrochlore second phases and an increase in the perovskite lateral grain size and columnarity. The occurrence and composition of Zr-rich (surface) pyrochlore phases were found to depend on Nb concentration, annealing temperature, and Pb content. The observed changes in ferroelectric and dielectric properties as a function of Nb dopant addition were found to be strongly influenced by microstructural effects and the occurrence of pyrochlore, and hence the intrinsic effects of Nb incorporation in the perovskite lattice could not be directly ascertained.