Well-preserved Mesozoic vertebrate fossils were found from lacustrine deposits interbedded with tuff and tuffites in the lower part of the Yixian Formation, western Liaoning Province, China. The fossil-rich layers were preserved in the intermediate-acid volcanic deposits in Sihetun excavating profile. Based on the petrographic studies of samples of the tuff and tuffites collected from the profile, this paper determines major element concentrations and volatile compositions of the melt inclusions in phenocrysts and matrix glasses with electron microprobe analysis. Volatile (S, F, Cl and H2O) contents emitted into the atmosphere were estimated by comparing pre- and post-eruptive volatile concentrations. Amount of volatiles (except for water) emitted in western Liaoning are much higher than those in the historic eruptions which had a substantial effect on climate and environment. Based on the nature and amount of the gases emitted in the eruptions of western Liaoning, we present a hypothesis that volatile-rich volcanism could result in mass mortality of vertebrates in the study area by injecting a large amount of volatiles (e.g., SO2, H2S, HCl, HF and H2O) into the stratosphere that would have triggered abrupt environmental and climate changes and altered lake chemistry. In terms of contents of volatile emissions, the eruptions in western Liaoning can be subdivided into the following three categories. The first group is dominated by HF emission, which had a fatal but possibly short-lived effect on paleoclimate and paleoenvironment and finally caused the mass mortality of the primitive birds. The second group presents the highest halogen concentrations emitted. However, contents of chlorine erupted is higher than those of fluorine emitted. The reactive chlorine compounds probably led to the ozone layer depletion and, therefore, caused mass mortality of most of all vertebrates including fishes, turtles and dinosaurs. The third one consists mainly of sulfur gases (primarily SO2 and H2S) released. They declined the surface’s temperatures and formed large-scale toxic acid rains. Eventually, such environmental trauma killed many land- and freshwater-based vertebrates and formed vertebrate (including feathered theropod dinosaurs) fossil-rich layers. The results show that the Mesozoic volcanic activities on either a large scale or frequent moderate scales in western Liaoning could lead to mass mortality of the vertebrates.