β-Chloroacrylonitriles constitute an important class of highly functionalized synthetic intermediates in organic chemistry due to the simultaneous presence of an activated carbon–carbon double bond, a chlorine atom, and a nitrile group. These complementary reactive functionalities confer exceptional synthetic versatility, making β-chloroacrylonitriles attractive precursors for the preparation of a broad range of biologically relevant heterocyclic compounds. In the present study, an efficient and sustainable microwave-assisted synthetic protocol was developed for the preparation of β-chloroacrylonitrile derivatives via the Vilsmeier–Haack reaction. The application of microwave irradiation ensured rapid and uniform energy transfer throughout the reaction medium, considerably accelerating the reaction process while enhancing the isolated yields of the desired products. This approach also simplified the experimental procedure, reduced energy consumption, and minimized reaction times, making it consistent with the principles of green chemistry. The synthesized β-chloroacrylonitrile derivatives were successfully characterized by FT-IR and 1H NMR spectroscopy, confirming the formation and structural integrity of the target molecules. Owing to their unique electronic properties and the presence of multiple reactive centers, these compounds represent versatile synthons for subsequent functionalization and cyclization reactions. They provide convenient access to structurally diverse sulfur- and nitrogen-containing heterocyclic scaffolds, which are widely recognized for their promising pharmaceutical and biological activities. Consequently, the developed microwave-assisted methodology offers a rapid, efficient, and environmentally friendly route for the synthesis of β-chloroacrylonitriles, providing valuable intermediates for the design and preparation of novel sulfur- and nitrogen-containing heterocyclic derivatives with potential applications in medicinal chemistry and advanced organic synthesis.