A novel type of deprotonative functionalization of aromatics was accomplished with a phosphazene base (t-Bu-P4 base). For various nitrogen heteroaromatics and benzene derivatives, deprotonative 1,2-additions proceeded with the t-Bu-P4 base and ZnI₂ as an additive in the presence of carbonyl compounds. The t-Bu-P4 base has both extremely strong Brønsted basicity and less nucleophilicity due to its huge, widely conjugated structure, and highly chemoselective deprotonations were achieved. In addition the nonmetallic t-Bu-P4 base should not function as a Lewis acid. Therefore the deprotonation with the t-Bu-P4 base is considered to proceed via a different pathway from traditional deprotonative metalation of aromatics with metallic bases. Some reactions with unique regioselectivities were observed.