A reliable process for the formation of nanoporous ZnO films supported on amorphous quartz and (100) silicon substrates via the processing of ZnO/Zn precursor films is reported. The process is based on the sublimation mechanism of Zn implemented in a novel ZnO/Zn precursor film to produce a nanoporous film. A scanning electron microscopy analysis of the nanoporous ZnO films’ surfaces revealed the presence of ZnO nano-features with round tips; in contrast, the nanoporous ZnO films supported on (100) Si substrates showed hexagonal nut-like nanostructures. The crystallite size of the nanoporous ZnO films decreased as the sublimation temperature was increased. X-ray photoelectron spectroscopy studies demonstrated that formations of oxygen vacancies were produced during the processing stages (as the main structural lattice defects in the ZnO nanoporous films). The analysis of the photoluminescence response confirmed that the active deep-level centers were also related to the oxygen vacancies generated during the thermal processing of the ZnO/Zn precursor films. Finally, a qualitative mechanism is proposed to explain the formation of nanoporous ZnO films on quartz and crystalline Si substrates. The results suggest that the substrates used have a strong influence on the nanoporous ZnO structures obtained with the Zn-sublimation-controlled process.