1,4‐Diazabicyclo2.2.2octane (dabco) and its derivatives have been extensively utilized as building units of excellent molecular ferroelectrics for decades. However, the homochiral dabco‐based ferroelectric remains a blank. Herein, by adding a methyl (Me) group accompanied by the introduction of homochirality to the H2dabco2+ in the non‐ferroelectric H2dabcoTFSA2 (TFSA=bis(trifluoromethylsulfonyl)ammonium), we successfully designed enantiomeric ferroelectrics R and S‐2‐Me‐H2dabcoTFSA2. The two enantiomers show two sequential phase transitions with transition temperature (Tc) as high as 405.8 K and 415.8 K, which is outstanding in both dabco‐based ferroelectrics and homochiral ferroelectrics. To our knowledge, R and S‐2‐Me‐H2dabcoTFSA2 are the first examples of dabco‐based homochiral ferroelectrics. This finding opens an avenue to construct dabco‐based homochiral ferroelectrics and will inspire the exploration of more eminent enantiomeric molecular ferroelectrics. The first examples of homochiral dabco‐based (dabco=1,4‐diazabicyclo2.2.2octane) ferroelectrics, R‐ and S‐2‐Me‐H2dabcoTFSA2 (TFSA=bis(trifluoromethylsulfonyl)ammonium), were designed from the non‐ferroelectric H2dabcoTFSA2. They show two phase transitions with a transition temperature (Tc) up to 405.8 K and 415.8 K, higher than the Tc of most dabco‐based or homochiral ferroelectrics.