In this study, we investigated the catalytic activity of bimetallic layered double hydroxide catalysts (M–Al–LDH) in the aldol condensation reaction between benzaldehyde (B) and 1–heptanal (H). Specifically, we used M–Al–LDH, where M represents magnesium (Mg), nickel (Ni), and zinc (Zn) with the same molar ratio of M/Al = 3, as heterogeneous basic catalysts for the aldol–condensation to produce jasminaldehyde (J). To prepare the M–Al–LDH catalysts, we employed the co-precipitation method using the nitrate precursors under a nitrogen atmosphere. Sodium hydroxide was used as the precipitating agent. The resulting solids were characterized using various techniques, including X-ray diffraction (XRD), Fourier-transform infrared spectroscopy (FT-IR), thermogravimetric analysis (TGA/DTA), and BET textural analysis, to study their structural properties. The performance of the catalysts was evaluated and compared in the aldol condensation reaction of benzaldehyde with 1–heptanal under solvent-free conditions, which were carried out in a microwave oven. We also investigated the influence of several reaction parameters on the conversion of 1–heptanal and the selectivity ratio (J/P) in detail to determine the optimal reaction conditions. The results obtained showed that the optimized Mg–Al–NO3 catalyst exhibited a higher conversion of 1–heptanal (99.7%) with a good selectivity ratio (J/P) of 4.00 compared to the other materials studied. Furthermore, the reaction proceeded rapidly in all cases, indicating the practicality of our protocol for the synthesis of jasminaldehyde.