Thin spray-on liner (TSL) is a surface protection technology used by spraying a polymer film, which is widely used for mine airtightness and waterproofing. A reinforcing TSL can replace steel mesh, which is a new method for roadway support. This paper reviews the development of a reinforcing TSL. Considering the deterioration of geological conditions in deep underground mining and the demand for reinforcing automation, two kinds of polymeric reinforcing TSL (RPTSL) materials are developed. The mechanical characteristics of the new TSL materials are studied experimentally. Results show that the average compressive strength, tensile strength, cohesion, and internal friction angle of the two TSL materials are 52 and 32 MPa, 12 and 8 MPa, 6.2 and 17.2 MPa, and 33.6° and 25.9°, respectively. The bonding strength between the two materials and coal is greater than the tensile strength of coal itself, and the mechanical properties of the material for comparison are lower than those of both materials. Based on the TSL support mechanism, we examine the application of the two TSL materials to the mining environment and compare the mechanical properties of polymer materials and cement-based materials. The advantages of polymer materials include versatile mechanical properties, good adhesion, and high early strength. This study provides a new support material to replace steel mesh for roadway surface support, which satisfies the needs of different surface support designs under complex geological conditions, and promotes the automation of roadway support.