This PDF file includes:

• Fig. S1. In-plane and out-of-plane resistivity of 3c-Fe₇Se₈.
• Fig. S2. Rietveld refinements of Li_xFe₇Se₈.
• Fig. S3. Electron diffraction patterns of 3c-Fe₇Se₈ and Li_0.89Fe₇Se₈ taken along 100 direction.
• Fig. S4. The plots of lnρ versus T^−1/ν+1 of Li_0.53Fe₇Se₈ from 2 to 10 K.
• Fig. S5. Resistivity of Li_0.53Fe₇Se₈ and Li_0.89Fe₇Se₈ at magnetic field of 0 and 8 T.
• Fig. S6. The room temperature reflectance and the real part of optical conductivity spectrum for Li_0.53Fe₇Se₈.
• Fig. S7. C_p/T versus T² plots of Li_xFe₇Se₈.
• Fig. S8. DOS of Li_xFe₇Se₈ for x = 0, 1/3, 2/3, and 1, respectively.
• Table S1. Summary of data collection and refinement parameters for Li_0.89Fe₇Se₈.

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