Efficient synthesis and catalysis of a series of palladium complexes having a group 13 metalloligand Ga, In) are reported utilizing 6,6 ''-bis(phosphino)terpyridine as a new scaffold for Pd-E bonds (E = Al, Ga, In). Systematic investigation revealed unique character, istics of the Al-metalloligand in both structure and reactivity, which exhibited the highest catalytic activity for hydrosilylation of CO2 ever reported (TOF = 19 300 h(-1)). This study demonstrated fine-tuning of catalyst activity by the precisely designed metalloligand is a promising approach for new catalyst development in synthetic organometallic chemistry.