The study of dynamic covalent chemistry (DCC) is growing rapidly in polymer chemistry. The dynamic covalent chemistry of polyaminals formed by the reaction of linear polyethyleneimine (L-PEI) with various functional aldehydes is explored. The study demonstrates the pH-dependent kinetics of polyaminal formation and the versatility of polyaminals in controlling the release of aldehydes under ambient conditions. Additionally, the controlled temperature-induced release of aldehydes and the dynamic shuffling behavior of aminals in polymer systems are investigated, emphasizing the potential for dynamic, covalently bonded polymers through dynamic aminal chemistry. The research showed the dynamic covalent aminal exchange for creating a range of new polymer materials.