The synthesis of carbon dots (CDs) from coal represents a promising strategy for advancing both the efficient, low-carbon utilization of coal resources and the cost-effective production of CDs. To enable the controlled, high-quality conversion of CDs from coal, a comprehensive understanding of the relationship between the coal chemical structure and the properties of CDs is crucial. This study prepared CDs from nine kinds of coal using a chemical oxidation method, and the correlations between properties of coal-based carbon dots and the original materials were revealed. The results show that the luminescence sites of coal-derived CDs are mostly distributed around 435 nm or 500 nm, where the former one relates to the confined sp² domains and the latter one is associated with the defect structure. Coal with a volatile content of about 20–30% in the nine samples was found to produce higher CD yields, with a maximum mass yield of 19.96%, accompanied by stronger fluorescence intensity. During chemical oxidation processes, the unsaturated double bonds (C=C, C=O) and aliphatic chains firstly break, and then aromatic clusters are formed by dehydrocyclization between carbon crystallites, followed by the introduction of a C–O group. The growth of the C–O group in the CDs contributes to a stronger fluorescence property. Furthermore, strong correlations were found between the carbon skeleton structure of raw coal and photoluminescence characteristics of corresponding CDs, as reflected by Raman parameters A_D1/A_G, I_D1/I_G, and FWHM_D. The findings offer significant insights into the precise modulation and control of coal-based carbon dot structures.