To investigate the effect of calcium mineral on the product distribution of low-rank coal pyrolysis, a Chinese subbituminous coal (Shenmu coal), and samples with 5% and 10% added calcium content, were selected to study with a homemade pyrolysis vacuum ultraviolet photoionization mass spectrometry (py-VUV-PIMS) system. In this system, secondary reactions of the pyrolysis products were generally inhibited because of in situ sampling, soft ionization, and high vacuum environment, which allowed direct detection of the initial pyrolytic products. Most evolved compounds during temperature programmed heating from 30 to 650 degrees C were ionized by a VUV lamp (10.6 eV). The main products indude five categories: alkenes, dienes, aromatics, phenols, and dihydroxy aromatics, which were formed via homolytic scission of weak bonds in side chains and bridges between aromatic nuclei in coal structure. The calcium mineral additives can dramatically affect pyrolytic product distribution, especially oxygen-containing compounds. The main reason is that calcium mineral plays a catalytic role in deoxygenation, which prompted incorporation of oxygen-containing compounds into corresponding aromatics, and resulted in the product of BTX levels increase significantly. The decrease in relative average molecular weight indicated the conversion of heavier components into lighter species, in terms of the observed m/z of the evolved gas components.