Self‐cleaning surface coatings is ubiquitous with variety of products today including glass and ceramic tiles, anti‐fogging mirrors, paints, mortars, and concrete. The phenomenon of self‐cleaning is attributed to superhydrophobic surface capable of cleaning itself without any human intervention. The development of superhydrophobic surfaces has been inspired by the desire to mimic the nature viz., water repellent property of lotus leaves and the process is termed as lotus effect. A variety of chemical and physical methods have been reported to fabricate of rough surfaces with low‐surface‐energy coating like, molecular assembly processes, chemical vapor deposition, sol–gel method, and breath‐figure technique (BFT) among others. Among them, BFT offers simple solution processability, robustness, and excellent tunability of surface architecture at different length scales. In this progress report, molecular architectonics of small functional molecules and its application in fabricating selfcleaning materials and surfaces through simple solution processing techniques is described. In these bioinspired approaches, self‐assembly properties of small functional molecules at the molecular level can be controlled by conjugating with basic biomolecules or biomimetic units as functional auxiliaries and adapting suitable experimental techniques. Overall, this progress report demonstrates the progress in molecular architectonics‐based approaches to develop superhydrophobic surfaces with self‐cleaning applications.