Sodium caseinate was chemically modified in order to alter its isoelectric point (pI). Negatively charged carboxylic groups were introduced to lower the pI, and positively charged amino groups to achieve the opposite. Different chemical amino acid modification approaches were studied and the modified proteins were characterized using free amino group assays, SDS−PAGE, MALDI-TOF mass spectrometry, and zeta potential measurements. Oil-in-water emulsions were prepared using these modified caseinates. The pH stability behavior of the emulsions was monitored, and interestingly, the stability of the emulsion could be modulated through steering the pI of caseinate. Using different modified caseinates, it was possible to create emulsions that were stable in the acid, neutral, and alkaline regions of the pH spectrum. The stability behavior of the emulsions correlated well with the theoretical and experimentally determined pI values of the caseinates. Storage stability of emulsions was also studied at pH values around 7, and emulsions made of modified caseinates showed storage stability similar to that of unmodified caseinate emulsions.