Although nanoparticles are widely used as catalysts, little is known about their potential ability to trigger privileged transfor-mations as compared to homogeneous molecular or bulk heterogeneous catalysts. We herein demonstrate (and rationalize) that nanoparticles display orthogonal reactivity to molecular catalysts in the cross-coupling of aryl halides with aryl germanes. While the aryl germanes are unreactive in LnPd(0)/LnPd(II) catalysis and allow selective functionalization of established coupling partners in their presence, they display superior reactivity under Pd nanoparticle conditions, outcompeting established coupling partners (such as e.g. ArBPin, ArBMIDA ) and allowing air-tolerant, base-free and orthogonal access to valuable and challenging biaryl motifs. As opposed to the notoriously unstable polyfluoroaryl and 2-pyridyl boronic acids, the corresponding germanes are highly stable and readily coupled. Our mechanistic and computational studies provide unambiguous support of nanoparticle catalysis and suggest that owing to the electron-richness of aryl germanes, they preferentially react via electrophilic-aromatic substitution, and in turn are preferentially activated by the more electrophilic nanoparticles.