Volatile species from pyrolysis of two kinds of bituminous coal, Huainan (HN) and Yima (YM), were investigated online with tunable synchrotron vacuum ultraviolet photoionization mass spectrometry (SVUV-PIMS). Mass spectra of products at different photon energies and temperatures were measured during the pyrolysis process. Some isomeric products can be characterized by the SVUV-PIMS based on their different ionization energies. Aromatic compounds are dominant pyrolysis products of these coal samples, while a number of aliphatic products were also observed. In comparison of these two coals, the HN coal probably has more condensed aromatic structures than YM coal. The different structures of the macromolecular network between HN and YM coals probably lead to different pyrolytic products at the same temperature. This work demonstrates the good performance of SVUV-PIMS in online analysis of complex coal pyrolysis.