After determining the optimal reaction conditions, we successfully synthesized a wide range of hindered dialkyl ethers using various tertiary alcohols. Initially, the tertiary alkyl alcohols with different chain lengths were evaluated, all of which reacted smoothly, yielding the corresponding hindered ethers in 54-75% (Figure ). Subsequently, the tertiary alcohols with multiple aryl rings, including highly congested triphenylmethanol, were suitable for the hindered ether synthesis (7d-9d). Additionally, the tertiary alcohols bearing functional groups such as chlorine, ketone, and ester were accommodated in our system, forming the corresponding hindered ethers (10d-12d). The cyclic tertiary alcohols, such as 2ethyl-2-adamantanol and 1-methylcyclopropan-1-ol, which had strong ring strain and significant steric hindrance, typically posed challenges for the etherification. However, our synthetic strategy successfully overcame these obstacles, enabling the etherification of cyclic tertiary alcohols containing three to six rings, including the adamantane ring (13d-18d). To broaden the applicability of our reaction, tertiary alcohols bearing active groups, such as pyridine, alkene, and alkyne, were evaluated and demonstrated excellent compatibility in our system, highlighting the versatility of the reaction (19d-25d). We further expanded the scope to include various secondary and primary alcohols with different functional groups, including amines (28d, 29d), cyclopropyl (31d), chlorine (36d), and alkene (37d) functionalities, all of which were well-tolerated (26d-37d). Notably, hydroxyl amino acid was also converted into product in acceptable yield (38d). Moreover, phenol, water, and benzoic acid were also suitable nucleophiles, forming valuable aryl/alkyl ether, alcohol, and ester (39d-41d). General reaction conditions: N-tosylhydrazone (0.2 mmol), alcohol (10.0 equiv.), DBU (2.0 equiv.), 1,4-Dioxane (0.8 mL), 40 W 427 nm Kessil lamps, room temperature, 16 h.