Periodic TiO2 nanorod arrays with hexagonal, nonclose-packed (hncp) arrangements are synthesized by pulsed laser deposition (PLD) using polystyrene colloidal monolayers as templates and with subsequent annealing in air. The hncp-array formation is governed by in situ volume shrinkage of amorphous TiO2 nanorods in the crystallizing process during annealing. The array periodicity can easily be tuned by different sphere sizes of the colloidal template, whereas-the distance between neighboring nanorods can be controlled by altering the background gas pressure during the PLD process, at a given periodicity for the nanorod array. Parameter- controlled growth is helpful for investigating and optimizing the parameter-dependent field-emission (FE) performance compared to both particle films and nanorod arrays with top aggregation. With an increase in periodicity of a hncp nanorod array, the field-enhancement factor decreases and the turn-on FE field increases. FE characteristics can be further enhanced by increasing the distance between adjacent nanorods while maintaining the same periodicity and a large distance display the best FE performance and could be highly valuable for designing field-emission devices based on these periodic nanorod arrays.