We investigated the influence of the surface microstructure and chemistry of sol-gel grown PbZr0.52Ti0.48O3 (PZT) on the electrical performance of PZT-based metal-insulator-metal (MIM) capacitors as a function of Pb precursor excess. Using surface-sensitive, quantitative X-ray photo- electron spectroscopy and scanning electron microscopy, we confirm the presence of ZrOx surface phase. Low Pb excess gives rise to a discontinuous layer of ZrOx on a (100) textured PZT film with a wide band gap reducing the capacitance of PZT-based MIMs whereas the breakdown field is enhanced. At high Pb excess, the nanostructures disappear while the PZT grain size increases and the film texture becomes (111). Concomitantly, the capacitance density is enhanced by 8.7%, and both the loss tangent and breakdown field are reduced by 20 and 25%, respectively. The role of the low permittivity, dielectric interface layer on capacitance and breakdown is discussed.