In this paper, a two-layer seven-core structural fiber (TLSCSF) is proposed to support and improve the propagation of more orbital angular momentum (OAM) mode beams, thus increasing the transmission capacity and spectrum efficiency (SE) of an optical communication system. The TLSCSF is composed of seven sub-cores, each containing two inner and outer layers of core rings and a central air hole. The two core rings are prepared using two materials with different doping concentrations. The supported OAM modes can be propagated in the fiber core ring. A finite element method (FEM) is used to analyze the designed fiber, and the calculated results show that the TLSCSF can stably transmit 322 OAM modes without higher order radial modes in the wavelength range of 1.5∼1.6 um. The corresponding effective refractive index difference between two adjacent vector modes (HE/EH) is more than 10−4. The measured effective mode areas (Aeff) and the confinement losses (CL) of HE or EH modes are larger than 54 um2 and smaller than 10−10 dB m−1, respectively. Moreover, the calculated dispersion variations and the mode qualities are lower than 230 ps nm−1 km−1 and more than 90%, respectively. Finally, the 10ps walk-off lengths of all vector modes supported by TLSCSF at a wavelength of 1.55 um are also evaluated, where the measured results show that except for HE2,1 and EH1,1, all other modes achieve a 10ps walk-off length of the order of 103 to 105. Consequently, the TLSCSF can contributes to improving the channel capacity and SE by supporting 322 fundamental radial OAM modes with robust performances in an optical communication system.