Carbon–carbon (C–C) coupling is critically important in organic synthesis. Direct C–C coupling to replace two C–H bonds is preferred over coupling of two prefunctionalized C–intermediates but is synthetically challenging. While such coupling is feasible through homogeneous catalysis, the mechanism regarding how the two C–H bonds are activated and coupled by heterogeneous active metal atoms remains not well understood. This work demonstrates the need for a proximate metal–metal dimer site to facilitate heterogeneously catalyzed C–C coupling reactions. We demonstrate that dinuclear Pd²⁺ sites in (Pd²⁺)₂-silicotungstate (Pd₂ST) catalyzed oxidative C–C coupling of 2-methylfuran by O₂ through synchronized double C–H activations under ambient conditions, selectively producing 5,5′-dimethyl-2,2′-bifuran (DMBF). Mononuclear Pd²⁺ ions in Pd₁H₂ST and H₄ST are not active. The ¹³C NMR and DRIFT spectroscopies of adsorbed ¹³CO, combined with DFT and theoretical ¹³C NMR calculations, determined that dinuclear Pd²⁺ ions are separated by ∼3.5 Å on Pd₂ST and 3.1 Å in the Pd²⁺—C(═O)—Pd²⁺ complex. XRD and TEM are used to confirm that the most active Pd₂ST/SiO₂ catalyst has near monolayer dispersion. ²⁹Si MAS NMR is used to confirm the presence of the silicotungstate structure after calcination. The original silicotungstate Keggin structure is maintained after the Pd₂ST/SiO₂ is calcined.