Pepper is widely grown all over the world, so it faces many abiotic stresses, such as drought, high temperature, low temperature, salt damage, and so on. Stresses causing the accumulation of reactive oxidative species (ROS) in plants are removed by antioxidant defense systems, and ascorbate peroxidase (APX) is an important antioxidant enzyme. Therefore, the present study performed genome-wide identification of theAPXgene family in pepper. We identified nine members of theAPXgene family in the pepper genome according to the APX proteins’ conserved domain inArabidopsis thaliana. The physicochemical property analysis showed thatCaAPX3had the longest protein sequence and the largest molecular weight of all genes, whileCaAPX9had the shortest protein sequence and the smallest MW. The gene structure analysis showed thatCaAPXswere composed of seven to 10 introns. TheCaAPXgenes were divided into four groups. TheAPXgenes of groups I and IV were localized in the peroxisomes and chloroplasts, respectively; the group II genes were localized in the chloroplasts and mitochondria; and the group III genes were located in the cytoplasm and extracell. The conservative motif analysis showed that allAPXgenes in the pepper had motif 2, motif 3, and motif 5. TheAPXgene family members were distributed on five chromosomes (Chr. 2, 4, 6, 8, and 9). Thecis-acting element analysis showed that mostCaAPXgenes contain a variety ofcis-elements related to plant hormones and abiotic stress. RNA-seq expression analysis showed that the expression patterns of nineAPXswere different in vegetative and reproductive organs at different growth and development stages. In addition, the qRT-PCR analysis of theCaAPXgenes revealed significant differential expression in response to high temperature, low temperature, and salinity stresses in leaf tissue. In conclusion, our study identified theAPXgene family members in the pepper and predicted the functions of this gene family, which would provide resources for further functional characterization ofCaAPXgenes.