A high rate all-optical secure communication scheme of chaotic multiple-quantum-well lasers from external injection light is studied. The system synchronization equation is derived. Synchronization is theoretically demonstrated and numerically achieved. Synchronization time is shortened and synchronization stability is boosted with the feedback coefficient increasing in numerical simulations. Models of all-light chaos masking and chaos shift keying modulation-demodulation with multiple-quantum-well lasers are investigated for secure communications, respectively. Chaos analog secure communication with a sinusoidal signal of 0.2 GHz modulation frequency, chaos digital secure communication with a digital signal of 20 Gb/s modulation rate and chaos shift keying secure communication with the modulation rate 0.05 Gb/s are numerically simulated, respectively. It is found that the system shows a good ability of robust and anti-code-breaking. Synchronous error is numerically calculated in chaos digital communications with the modulation bandwidth of 20 Gb/s in the modulation-demodulation processes and the modulation rate characterization is analyzed to conclude that lower synchronous error under high bit rate and the maximum bit rate limit of 1 Gb/s in chaos shift keying communication.