Tea standard samples are the benchmark for tea product quality control. Understanding the inherent differences in Chinese national standards for Lapsang Souchong black tea of different grades is crucial for the scientific development of tea standardization work. In this study, Lapsang Souchong black tea of different grades that meet Chinese national standards was selected as the research object. The aroma characteristics were comprehensively analyzed through sensory evaluation, electronic nose, and HS-SPME-GC-MS (headspace solid-phase microextraction gas chromatography–mass spectrometry). The findings indicate that the higher-grade Lapsang Souchong has a higher evaluation score. The results of electronic nose analysis indicate that the volatiles with differences in tea of different grades were mainly terpenoids and nitrogen oxides. The results of HS-SPME-GC-MS analysis show that the odor characteristics of the super-grade samples are mainly floral and fruity, and these substances mainly include D-Limonene, 3,7-dimethyl-1,6-octadien-3-ol and 3-Hydroxymandelic acid, and ethyl ester. The primary aroma characteristics of the first-grade samples are floral, sweet, woody, and green, with key contributing compounds including 2-Furanmethanol, 1-Octen-3-ol, and 5-ethenyltetrahydro-α,α,5-trimethyl-cis-, 4,5-di-epi-aristolochene. The main aroma characteristics of the second-grade samples are green, herbal scent, and fruity, and the main substances include 3,7-dimethyl-1,6-octadien-3-ol, 2,3-dimethylthiophene, Dihydroactinidiolide, and Naphthalene-1-methyl-7-(1-methylethyl)-. It is worth noting that the second-grade samples contain a large amount of phenolic substances, which are related to the smoking process during processing. This study lays a solid foundation for the preparation of tea standard samples and the construction of the tea standard system.