In this paper, a kind of metastructure–photonic crystal (MPC) with multi-frequency asymmetric absorption–transmission properties is proposed. It is composed of various dielectric layers arranged in a periodically tilting pattern. When electromagnetic waves (EMWs) enter from the opposite direction, MPC shows an obvious asymmetry. EMWs are absorbed at 13.71 GHz, 14.37 GHz, and 17.10 GHz in forward incidence, with maximum absorptions of 0.919, 0.917, and 0.956, respectively. In the case of backward incidence, transmission above 0.877 is achieved. Additionally, the MPC is utilized for refractive index (RI) sensing, allowing for wide RI range detection. The refractive index unit is denoted as RIU. The RI detection range is 1.4~3.0, with the corresponding absorption peak variation range being 17.054~17.194 GHz, and a sensitivity of 86 MHz/RIU. By adjusting the number of MPC cycles and tilt angle, the sensing performance and operating frequency band can be tailored to meet various operational requirements. This MPC-based RI sensor is simple to fabricate and has the potential to be used in the development of high-performance and compact sensing devices.