Cs–pollucite can be a potential solid base catalyst due to the presence of (Si-O-Al)⁻Cs⁺ basic sites. However, it severely suffers from molecular diffusion and pore accessibility problems due to its small micropore opening. Herein, we report the use of new organosilane, viz. dimethyloctadecyl[3-(trimethoxysilyl)propyl]ammonium chloride (TPOAC), as a promising pore-expanding agent to develop the hierarchical structure in nanosized Cs–pollucite. In respect to this, four different amounts of TPOAC were added during the synthesis of hierarchical Cs–pollucite (CP-x, x = 0, 0.3, 1.0, or 2.0, where x is the molar ratio of TPOAC) in order to investigate the effects of TPOAC in the crystallization process of Cs–pollucite. The results show that an addition of TPOAC altered the physico-chemical and morphological properties of hierarchical Cs–pollucite, such as the crystallinity, crystallite size, pore size distribution, surface areas, pore volume, and surface basicity. The prepared solids were also tested in Claisen–Schmidt condensation of benzaldehyde and acetophenone, where 82.2% of the conversion and 100% selectivity to chalcone were achieved by the CP-2.0 catalyst using non-microwave instant heating (200 °C, 100 min). The hierarchical CP-2.0 nanocatalyst also showed better catalytic performance than other homogenous and heterogeneous catalysts and displayed a high catalyst reusability with no significant deterioration in the catalytic performance even after five consecutive reaction runs.