This study aimed to explore the applicability of DNA barcoding for assessing the authenticity of caviar on the Chinese market. A set of universalCOIprimers and two sets of designed primers based onCOIandD-loopgenes were used to identify maternal species of samples from 21 batches of caviar. The results showed that the PCR products from three sets of primers had more than 98% similarity to the sequences in database. TheCOIgene could not distinguish sturgeons with closed genetic relationships, whileD-loopgene could effectively improve the accuracy of DNA barcoding and was more suitable to the identification of interspecific sturgeon than theCOIgene. The neighbor-joining dendrogram further confirmed the applicability and accuracy ofCOIandD-loopgenes in identifying maternal relatives of caviar (Acipenser baerii/Acipenser gueldenstaedtii/Acipenser schrenckii/Huso dauricus/Huso huso). Despite the limitations of mitochondrial DNA in identifying hybrid sturgeon species, the presence of counterfeit caviar of non-sturgeon ingredients could be excluded. All the caviar samples were identified successfully as sturgeon species, but the mislabeling rate of species was 33.4%, indicating that there were illegal phenomena such as disorderly labeling, mislabeling, and adulteration on the market.