Heavy crude oil has poor solubility and a high density, making recovery and transport much more difficult and expensive than for light crude oil. Emulsifiers can be used to produce low viscosity oil-in-water emulsions for recovery and transport, but subsequent demulsification can be challenging. Here, we develop and implement interfacially active, pH-responsive polymer-coated nanoparticles (PNPs) to reversibly stabilize, recover, and break oil/water emulsions through variation of solution pH. Silica particles with poly(2-(dimethylamino)ethyl methacrylate) (DMAEMA) chains covalently grafted to the surface are prepared although a reversible addition fragmentation chain transfer grafting-through technique. The resulting DMAEMA PNPs can stabilize emulsions of high viscosity Canadian heavy oil at PNP concentrations as low as 0.1 wt % and at neutral pH. The performance of the DMAEMA PNPs exceeds that of DMAEMA homopolymer additives, which we attribute to the larger size and irreversible adsorption of DMAEMA PNPs to the oil/water interface. After recovery, the emulsion can be destabilized by the addition of acid to reduce pH, resulting in separation and settling of the heavy oil from the aqueous phase. Recovery of more than 10 wt % of the crude heavy oil-in-place is achieved by flooding with aqueous solution of 0.1 wt % DMAEMA PNPs without any additional surfactant or chemical. This work demonstrates the applicability of PNPs as surface active materials for enhanced oil recovery processes and for heavy oil transport.