The application belongs to the technical field of fiber lasers, and in particular relates to a composite thin film, a preparation method thereof, and a self-starting mode-locked fiber laser device. Because the gain fiber doped with rare earth atoms is expensive, the cost of the fiber laser is also very high. At the same time, the long gain fiber will lead to extremely obvious Kelly sidebands of the mode-locked pulse, which will eventually cause the interaction between soliton pulses, resulting in The timing jitter of pulses aggravates the bit error rate of long-distance communication, which is not conducive to the improvement of communication quality. The application provides a composite film, which is composed of the following raw materials in parts by weight: 3-11 parts of polyvinylpyrrolidone, 16-24 parts of ethylene glycol, 76-84 parts of sodium hydroxide, 2-2 parts of bismuth chloride 10 parts, 1 to 9 parts of antimony chloride and 11 to 19 parts of sodium tellurite. It has weak Kelly sidebands, high damage resistance threshold, can realize self-starting mode locking, easy to operate, narrow pulse, and good stability.