The composition characteristics of altered coals in the Huaibei Coalfield, China, was investigated through a comparative analysis between altered and unaffected coals from the Wolonghu, Taoyuan and Renlou coal mines. Results indicated that the altered coals in Wolonghu coal mine are mostly anthracite coals, with a maximum vitrinite reflectance of 1.6–3.9% (average of 2.9%). Coals from Wolonghu coal mine were mainly consisted of vitrinite (66.2–97.0%), followed by inertinite (2.0–4.0%) and exinite (0.4–6.9%). Differences in volatile matter content were observed between the altered coals in Wolonghu coal mine and unaffected coals from neighboring coal mines, implying that the chemical composition and maturity of coals were changed after magmatic alteration. In addition, differences in hydrogen element were noted among the coals from Wolonghu, Renlou and Taoyuan coal mines, and the phenomenon of “deficient in hydrogen element” was observed in Wolonghu coals. The aliphatic hydrocarbon structure parameters suggested that the aliphatic chain lengths of Wolonghu coals are shorter than those of coal samples from the Renlou and Taoyuan coal mines. In addition, maturity is positively correlated with hydrogen enrichment degree, but negatively related with aliphatic hydrocarbon structure. Coals from Renlou and Taoyuan coal mines showed great weight loss with various heating rates at temperatures of 0–1000 °C, whereas those from Wolonghu coal mine had less weight loss.