Titanium dioxide (TiO2) attracts extensive attention due to its widespread technological and environmental applications. This study seeks to investigate the surface charging behavior of the two TiO2 polymorphs, anatase and rutile, using Flow Adsorption Microcalorimetry (FAMC). FAMC allows direct quantitative measurement of the heat of a surface reaction; these calorimetric heats are directly proportional to the surface charge. Determining the magnitude of positive and negative charges at the surface over a range of pHs allows for the determination of the point of zero net charge (PZNC) via a unique calorimetric method that removes many of the shortcomings related to the other analytical techniques used for such measurements.