Acid catalysts play a vital role in the industrial synthesis and production of a plethora of organic chemicals. But, their subsequent neutralization and disposal is also a giant source of waste. For example, for a Friedel-Crafts acylation with AlCl 3, a kilogram of product yields up to 20 kg of (contaminated) waste salt. Other processes are even worse, and this waste is both an environmental and economic shortcoming. Here we address this issue by showing a series of acid catalysts where the neutralization is "built in" to the system and thus eliminates waste. Clearly these will not replace all organic and mineral acid catalysts, but they can replace many. Further, we show how these self-neutralizing catalysts can often eliminate unwanted byproducts, improve selectivity, or elimination of mass transfer limitations by changing from heterogeneous to homogeneous systems. They readily facilitate separations and promote recycling, to promote both green chemistry and good economics. First is near-critical water, or liquid water under pressure, where the K W for dissociation goes up 3-4 decades between 0 degrees C and 250 degrees C, thus facilitating both acid and base catalysis. Moreover, as the exothermic hydrogen bonding diminishes, the dielectric constant goes down to the point at which both salts and organics are soluble in this very hot water. For example, toluene and water are completely miscible at 305 degrees C. This eliminates mass transfer limitations for the reactions, and postreaction cooling not only lowers the K W to neutralize the ions without waste but also results in facile separations from simple liquid-liquid immiscibility. Further, we show the formation of catalysts with alkylcarbonic acids from alcohols and CO2, analogous to carbonic acid from water and CO2. We show a number of applications for these self-neutralizing catalysts, including the formation of ketals, the formation of diazonium intermediates to couple with electron-rich aromatics to produce dye molecules, and the hydration of beta-pinene. Here also these systems often enhance phase behavior to cut mass transfer resistance. In an analogous application we show that peroxide and CO2 gives peroxycarbonic acid, also reversible upon the removal of the CO2, and we show application to epoxidation reactions. The bottom line is that these catalysts afford profound advantages for both green chemistry and improved economics. The methods outlined here have potential for abundant applications, and we hope that this work will motivate such opportunities.