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NAC (NAM, ATAF1/2, and CUC2) transcription factors (TFs) are one of the largest plant-specific TF families and play a pivotal role in adaptation to abiotic stresses. The genome-wide analysis of NAC TFs is still absent in <i>Zanthoxylum bungeanum</i>. Here, 109 ZbNAC proteins were identified from the <i>Z. bungeanum</i> genome and were classified into four groups with <i>Arabidopsis</i> NAC proteins. The 109 <i>ZbNAC</i> genes were unevenly distributed on 46 chromosomes and included 4 tandem duplication events and 17 segmental duplication events. Synteny analysis of six species pairs revealed the closely phylogenetic relationship between <i>Z. bungeanum</i> and <i>C</i>. <i>sinensis</i>. Twenty-four types of <i>cis</i>-elements were identified in the <i>ZbNAC</i> promoters and were classified into three types: abiotic stress, plant growth and development, and response to phytohormones. Co-expression network analysis of the <i>ZbNAC</i>s revealed 10 hub genes, and their expression levels were validated by real-time quantitative polymerase chain reaction (qRT-PCR). Finally, <i>ZbNAC007</i>, <i>ZbNAC0</i><i>18</i>, <i>ZbNAC047</i>, <i>ZbNAC072</i>, and <i>ZbNAC079</i> were considered the pivotal NAC genes for drought tolerance in <i>Z. bungeanum</i>. This study represented the first genome-wide analysis of the NAC family in <i>Z. bungeanum</i>, improving our understanding of NAC proteins and providing useful information for molecular breeding of <i>Z. bungeanum</i>.