The minimum energy conformations and racemization barriers for the chiral sterically overcrowded helical alkenes, trans- and cis-1,1',2,2',3,3',4,4'-octahydro-4,4'-biphenanthrylidenes (1 and 2), are reported. The trans-1 and cis-2 isomers can each adapt three different conformations, (P,P) and (M,M) (an enantiomeric pair) and an achiral (P,M) meso form, of which only the chiral isomers were obtained by synthesis. The conformations and heats of formation of (M,M)-(E)-1, (P,M)-(E)-1, (M,M)-(Z)-2, and (P,M)-(Z)-2 isomers were determined by MOPAC AM1 calculations. The racemization process for both the trans- and cis- isomers is postulated to occur via the (P,M) isomers by two successive inversions of the cyclohexenyl ring; (M,M) ↔ (P,M) ↔ (P,P). The (M,M) → (P,M) and reverse (P,M) → (M,M) isomerizations were simulated by reaction path calculations, providing the molecular structure and the activation energy of the transition state for each isomerization. For each racemization process, the activation enthalpy (ΔH‡) was calculated as 23.9 and 19.9 kcal mol-1 for trans-olefin 1 and cis-olefin 2, respectively. These values reasonably agree with the experimental values obtained by temperature-dependent circular dichroism, optical rotation, and 1H NMR magnetization transfer measurements: ΔH‡ = 24.6 and 20.8 kcal mol-1 for trans-olefin 1 and cis-olefin 2, respectively. While the racemization of cis-isomer 2 is controlled by the steric interaction of H5 with C4'a and C4'b, the surprisingly high barrier for trans-olefin 1 is due to the severe steric interaction between H5 and H3'α and/or H3'β protons.