Optical chaotic signals emitted from an external-cavity feedback or injected laser diode enable small-signal information concealment in a noise-like carrier for secure optical communications. Due to the chaotic bandwidth limitation resulting from intrinsic relaxation oscillation frequency of lasers, multiplexing of optical chaotic signal, such as wavelength division multiplexing in fiber, is a typical candidate for high-capacity secure applications. However, to our best knowledge, the utilization of the spatial dimension of optical chaos for free-space secure communication has not yet been reported. Here, we experimentally demonstrate a free-space all-optical chaotic communication system that simultaneously enhances transmission capacity and security by orbital angular momentum (OAM) multiplexing. Optical chaotic signals with two different OAM modes totally carrying 20 Gbps on–off keying signals are secretly transmitted over a 2 m free-space link, where the channel crosstalk of OAM modes is less than −20 dB, with the mode spacing no less than 3. The receiver can extract valid information only when capturing approximately 92.5% of the OAM beam and correctly demodulating the corresponding mode. Bit error rate below the 7% hard-decision forward error correction threshold of 3.8×10−3 can be achieved for the intended recipient. Moreover, a simulated weak turbulence is introduced to comprehensively analyze the influence on the system performance, including channel crosstalk, chaotic synchronization, and transmission performance. Our work may inspire structured light application in optical chaos and pave a new way for developing future high-capacity free-space chaotic secure communication systems.