The size effect of the CoxMn1−xO precursor on the formation of Co2C nanoprisms and the structure–performance relationship for the Fischer–Tropsch to olefins (FTO) reaction was investigated. CoxMn1−xO precursors with different sizes from 6.5 nm to 16.7 nm were fabricated by calcination at different temperatures. The CoxMn1−xO with small size possessed high concentration of oxygen vacancies, which promoted the dissociation of CO to form active C* species, and more Co2C nanoprisms with small size could be generated. In addition, the catalytic performance also changed with the size of the precursor. The olefin formation rate significantly increased from 3.36 to 12.48 μmol gCoxMn1−xO−1 h−1 as the CoxMn1−xO size decreased from 16.7 to 6.5 nm. This work clearly elucidates the size effect of the CoxMn1−xO precursor on the structure–performance relationship and may provide a practical and simple strategy to fabricate highly efficient CoMn catalysts for the FTO reaction.