The scattering from air–glass interfaces within solid-core polarization-maintaining photonic crystal fiber (PM–PCF) will increase the fiber attenuation coefficient, which may lead to high transmission loss. Therefore, it is necessary to describe scattering properties to guide research into reducing fiber loss. In this paper, the loss resulting from roughness scattering at multi-hole interfaces within PM–PCF was theoretically and experimentally analyzed. A PM–PCF scattering model was established to explore the scattering distribution. On the other hand, a fully automatic testing device was built to enable the measurement of a three-dimensional scattering sphere. Simulations were in good agreement with experimental measurements. Moreover, this new proposed measurement method could apply to other PCFs and it will be a useful tool for further scattering research.