This paper proposes a highly secure image encryption technique based on chaotic synchronization. Firstly, through the design of a synchronization controller, we ensure that the master–slave chaotic extremum-coded random number generators (ECRNGs) embedded in separated transmitters and receivers are fully synchronized to provide synchronized dynamic random sequences for image encryption applications. Next, combining these synchronized chaotic sequences with the AES encryption algorithm, we propose an image segmentation and multi-encryption method to enhance the security of encrypted images and realize a secure image transmission system. Notably, in the design of the synchronization controller, the transient time before complete synchronization between the master and slave ECRNGs is effectively controlled by specifying the eigenvalues of the matrix in the synchronization error dynamics. Research results in this paper also show that complete synchronization of ECRNGs can be achieved within a single sampling time, which significantly contributes to the time efficiency of the image transmission system. As for the image encryption technique, we propose the method of image segmentation and use the synchronized dynamic random sequences generated by the ECRNGs to produce the keys and initialization vectors (IVs) required for AES-CBC image encryption, greatly enhancing the security of the encrypted images. To highlight the contribution of the proposed segmented image encryption, statistical analyses are conducted on the encrypted images, including histogram analysis (HA), information entropy (IE), correlation coefficient analysis (CCA), number of pixels change rate (NPCR), and unified average changing intensity (UACI), and compared with existing literature. The comparative results fully demonstrate that the proposed encryption method significantly enhances image encryption performance. Finally, under the network transmission control protocol (TCP), the synchronization of ECRNGs, dynamic keys, and IVs is implemented as well as segmented image encryption and transmission, and a highly secure image transmission system is realized to validate the practicality and feasibility of our design.