Co2C-based catalysts with SiO2, γ-Al2O3, and carbon nanotubes (CNTs) as support materials were prepared and evaluated for the Fischer-Tropsch to olefin (FTO) reaction. The combination of catalytic performance and structure characterization indicates that the cobalt-support interaction has a great influence on the Co2C morphology and catalytic performance. The CNT support facilitates the formation of a CoMn composite oxide during calcination, and Co2C nanoprisms were observed in the spent catalysts, resulting in a product distribution that greatly deviates from the classical Anderson-Schulz-Flory (ASF) distribution, where only 2.4 C% methane was generated. The Co3O4 phase for SiO2-and γ-Al2O3-supported catalysts was observed in the calcined sample. After reduction, CoO, MnO, and low-valence CoMn composite oxide were generated in the γ-Al2O3-supported sample, and both Co2C nanospheres and nanoprisms were identified in the corresponding spent catalyst. However, only separated phases of CoO and MnO were found in the reduced sample supported by SiO2, and Co2C nanospheres were detected in the spent catalyst without the evidence of any Co2C nanoprisms. The Co2C nanospheres led to a relatively high methane selectivity of 5.8 C% and 12.0 C% of the γ-Al2O3-and SiO2-supported catalysts, respectively. These results suggest that a relatively weak cobalt-support interaction is necessary for the formation of the CoMn composite oxide during calcination, which benefits the formation of Co2C nanoprisms with promising catalytic performance for the sustainable production of olefins via syngas.