The catalytic effect of alkali-metal tert-butoxide clusters on the rate of ester interchange for several pairs of esters has been determined in nonpolar and weakly polar solvents. Reactivities increase in the order (Li+ < Na+ < K+ < Rb+ < Cs+) with the fastest rates reaching 10(7) catalytic turnovers per hour (TO/h). Ester interchange rates were sensitive to the size of both the transferring OR groups and the ester substituent. Phenyl esters did not exchange with aliphatic esters due to nonstatistical breakdown patterns in the tetrahedral intermediate. A first-order equilibration analysis on the interchange between tert-butyl acetate (tBuAc) and methyl benzoate (MeBz) (5 mol % NaOtBu) indicated enhanced reaction rates as the reaction proceeded. Isolation and quenching (DCl/D2O) of precipitated catalyst points to a mechanism whereby sequential methoxy incorporation into the catalyst cluster increases activity, but eventually precipitates out of solution as a 3:1 OMe:OtBu cluster. The rate law was determined to be k(obs)[MeBz](1) [tBuAc](0)[NaOtBu](x), where x = 1.2(1), 1.4(1), and 0.85(1) in hexane, ether, and THF, respectively, under conditions when tetrameric catalyst aggregates are expected. Reaction rates were generally observed to be higher in nonpolar solvents (hexane > toluene, ether > THF). Eyring analysis over a 40 degrees C range yielded Delta H-double dagger = 10.0(1) kcal mol(-1) and Delta S-double dagger = -32(3) eu. A Hammett (sigma) plot generated with para-substituted methyl benzoates gave rho = +2.35 (R = 0.996). These results are interpreted in terms of a catalytic cycle composed of two coupled transesterification reactions with a turnover-limiting addition of a tert-butoxy-containing cluster (tetramer) to methyl benzoate. Catalyst relative reactivities (Cs+ > Rb+ > K+ > Na+ > Li+) are interpreted in terms of competitive electrostatic interactions between the alkali-metal and ground-state and transition-state anions. This analysis predicts the observed linear dependence between log(k(obs)) and 1/r(ionic).