The data rate in a single-mode fiber is approaching the capacity limit given by the Shannon theory. Mode division multiplexing, such as few modes, orbital angular momentum, and cylindrical vector beam (CVB) multiplexing, has shown great potential to further increase data capacity in both free-space and fiber communication. We propose and demonstrate high-order CVB multiplexing communication in an air-core photonics crystal fiber (PCF). The simulation results show that the 19-cell air-core PCF supports transmission of CVB modes from ±1 to ±4 orders. In the experiment, ±1- to ±4-orders CVBs are transmitted in 8.25-m-long air-core PCF with the mode purities higher than 76.5%. We demonstrate four coaxial CVB channel communication by multiplexing the ±2- and ±3-orders CVB modes. Each CVB channel carries 10-Gbit/s on–off keying signals and the measured bit error rates satisfy the forward error correction threshold. CVB communications based on air-core PCF can be used in short-distance optical communication with high capacity and low optical latency.