The facile synthesis of ethers has long been a task in drug design, as the incorporation of the ether group enhances the solubility and bioavailability, thereby improving the druggability. The hindered dialkyl ethers can aid in the escape-from-flatland of bioactive molecules and improve the drug-target interaction to promote the drug efficacy and selectivity. Moreover, the polyfluorinated dialkyl ethers exhibit the improved lipophilicity and metabolic stability compared to their non-fluorinated counterparts. Notably, the polyfluorinated ethers are integral for enhancing the performance of lithiumbased batteries. Therefore, the practical and straightforward synthesis of the hindered and polyfluorinated dialkyl ethers has significant value in pharmaceutical and chemical industries. Nowadays, the Williamson ether synthesis and Mitsunobu reactions have proven to be reliable for accessing ethers, particularly primary dialkyl ethers. Recent decades have also seen the advancements in C-H activation, cyclopropane ring opening reactions, transition-metal catalysis , and other methodologies. Despite these improvements, the synthesis of the hindered dialkyl ethers remains challenging because of the bulkiness of reagents and competitive side reactions such as halide elimination.