Synthesis of Li+-selective 14-crown ether (CE) having rigid and bulky subunits was reported. CE-poly(vinyl alcohol) (PVA) dope solutions were electrospun. CEs were immobilized on PVA matrix via acid-catalyzed acetalization using novel aerosol method. Structures of new compounds and their immobilization to PVA were confirmed and characterized. Adsorption experiments show superior lithium capacity and selectivity among previously reported solid-supported CEs. Dihydroxy-dibenzo-14-crown-4 ether-PVA nanofiber membrane showed superior performance. This research was supported by Basic Science Research Program through the National Research Foundation of Korea (NRF) funded by the Ministry of Science, ICT and future Planning (2015R1A2A1A15055407) and Ministry of Education (2009-0093816).