Oxidation processes of coal surfaces are both fundamental and interesting from academic and engineering points of view. In this work, we comprehensively analyzed the mechanism of heating oxidation at 200 °C on the surface/interface characters and the floatability of anthracite coal. The variations of surface/interface characters were studied using SEM (scanning electron microscopy), FTIR (Fourier transform infrared spectroscopy), and XPS (X-ray photoelectron spectroscopy). The floatability was further identified using Induction Time and Bubble-Particle Wrap Angle. It was found that, after heating oxidation at 200 °C, both surface ravines and oxygen-containing groups were increased. The degradation of hydroxyl on anthracite could be neglected during the heating, while the oxidation of hydrocarbon chains dominated the balance of hydrophobicity and hydrophilicity on coal surface. The induction time significantly increased from 200 ms to 1200 ms and 2000 ms after 10 h and 20 h of heating oxidation at 200 °C, respectively. Additionally, raw coal exhibited the fastest kinetics of bubble-particle attachment and the largest wrap angle, directly proving that the floatability decreased after oxidation.