The demand-supply gap for light olefins and aromatics has been enormous in recent years. This imbalance is anticipated to grow exponentially due to their extensive use in manufacturing plastics, textiles, pharmacological intermediates, climate-neutral synthetic fuels, and hydrogen carriers. Production of light olefins through the catalytic cracking of naphtha is widely regarded as one of the most prestigious methods. Despite this, selecting an effective and efficient catalyst is one of the most challenging aspects of the scaling-up process. In this study, a highly active, modified MCM-22 catalyst has been synthesized by a hydrothermal method. Various techniques are used for the characterization of catalysts, including scanning electron microscopy (SEM), X-ray diffraction (XRD), N2 adsorption-desorption, temperature-programmed desorption of ammonia (NH3-TPD), and solid-state nuclear magnetic resonance experiments (NMR) with Al and Si. The cracking of n-dodecane to lower olefins was performed, and it was found that the conversion rates were highly correlated with the SiO2/Al2O3 ratio of the MCM-22 samples. Sample Si0.5 (SiO2/Al2O3 ∼ 28.9) showed a typical photograph of the MWW phase with a bran or flake shape in a stacking mode. The Si0.5 sample has a superior external surface area than other samples (up to ca. 130 m2/g) caused by a smaller particle with an average crystal size of around 15 nm, resulting in maximum catalytic performance towards light olefins. It was discovered that Si0.5 had a diminishing tendency in the paraffinic selectivity but had a robust selectivity for olefins (propylene and butylene in particular). This research may provide academics and the industry with new prospects for improving the catalytic cracking of n-dodecane into light olefins.