Laminated composite materials are formed by laminating two or more layers of the same or different materials. Due to the excellent mechanical properties, laminate composite materials are widely used in aerospace and navigation fields. However, during the production and service stage, defects such as disbond and delamination between, layers have greatly affected the stability of component. Currently, the commonly used contact ultrasonic testing has limitations such as large blind area, small field of view, many artifacts and water coupling. Combining the advantages of laser ultrasound and air-coupled ultrasound, a non-contact laser ultrasonic testing system consisting of eight elements 250 kHz air-coupled transducer is developed to detect thin laminated composite materials with thickness of 0.8 mm metal–carbon fiber and 0.3 mm metal–metal, respectively. The system can not only clearly display multiple disbond defects inside the sample, but also successfully identify micro cavity defects formed by bonding layer indentation and bubbles. The imaging field and SNR are up to 220 mm and 35 dB, respectively. Besides, compared to high-frequency phased array and X-ray testing, the system exhibits excellent imaging contrast, resolution, and sensitivity. The experimental results show that the developed large-field air-coupled laser ultrasonic testing system has broad application prospects in the large laminated composite materials.