For complex-valued or quaternionic neural networks, scholars and researchers usually decompose them into real-valued systems. The decomposed real-valued systems are equivalent to original systems. Then, the dynamical behaviors of real-valued systems obtained are investigated, including stability, synchronization, and chaos etc. In this paper, a class of quaternionic neural networks with time-varying delays is investigated. First, by designing a suitable PI controller, synchronization of the considered chaotic system is realized. By using a non-decomposition method and structuring a novel Lyapunov functional, sufficient conditions are derived to guarantee synchronization between the drive-response systems. It is worth mentioning that, unlike other methods, our approach does not require breaking down the quaternionic neural networks into four separate real-valued systems. Furthermore, we demonstrate the practical application of these chaotic quaternionic neural networks with time-varying delays in image encryption and decryption. Based on one sequence of chaotic signal from state trajectory of single quaternion-valued neuron and a new encryption algorithm, the application of chaotic system proposed, that is, image encryption, is researched. The process of image decryption is simply the reverse of the encryption process. Finally, numerical simulation examples are provided to validate the effectiveness of the designed PI controller and performance of image encryption and decryption.