Abstract: The low permeability of plastic layer of coking coal causes the formation of coking pressure, and the evolution of permeability is closely related to the release behavior of volatiles. In this paper, a low-volatile bituminous coal C1 and a high-volatile bituminous coal C2 were selected as research objectives, and a lignite L1 and two semi-cokes produced from the pyrolysis of C2 at two temperatures were used as the contrast. The permeability tests of single coal, binary coal or semi-coke and separated combination were conducted. The influence of volatiles release behaviors on the evolution of permeability of plastic layer was revealed by thermogravimetric and fluidity analyses. The results showed that there was a low permeability plateau stage of plastic layer of C1, while the permeability of plastic layer of C2 was rapidly improved after reaching the lowest. This was related to the difference in the mass transfer conditions of volatiles from two coals. C2 could enhance the mass transfer driving force of volatiles and bring both inert components (semi-coke after pyrolysis) and transferable hydrogen, thus the permeability of plastic layer could be improved without destroying the stability of plastic layer. The hydrogen-rich volatiles released from C2 before its initial softening temperature helped the low permeability of the plastic layer of C1 be formed and reach the maximum. The volatiles released during the plastic stage of C2 helped maintain the low permeability plateau of plastic layer of C1. It was plausible to further improve the permeability of plastic layer of C1 by consuming part of hydrogen-rich volatiles from C2 with prolonging the volatiles’ reaction. This paper provided a new insight in selecting high-volatile coals for improving permeability of the plastic layer from the aspect of volatiles’ release behaviors.