The pH of a solution is one of its most fundamental chemical properties, impacting reaction pathways and kinetics across every area of chemistry. The atmosphere is no different, with the pH of the condensed phase driving key chemical reactions that ultimately impact global climate in numerous ways. The condensed phase in the atmosphere is comprised of suspended liquid or solid particles, known as the atmospheric aerosol, which are differentiated from cloud droplets by their much smaller size (primarily <10 μm). The pH of the atmospheric aerosol can enhance certain chemical reactions leading to the formation of additional condensed phase mass from lower volatility species (secondary aerosol), alter the optical and water uptake properties of particles, and solubilize metals that can act as key nutrients in nutrient-limited ecosystems or cause oxidative stress after inhalation. However, despite the importance of aerosol acidity for climate and health, our fundamental understanding of pH has been limited due to aerosol size (by number >99% of particles are <1 μm) and complexity. Within a single atmospheric particle, there can be hundreds to thousands of distinct chemical species, varying water content, high ionic strengths, and different phases (liquid, semisolid, and solid). Making aerosol analysis even more challenging, atmospheric particles are constantly evolving through heterogeneous reactions with gases and multiphase chemistry within the condensed phase. Based on these challenges, traditional pH measurements are not feasible, and, for years, indirect and proxy methods were the most common way to estimate aerosol pH, with mixed results. However, aerosol pH needs to be incorporated into climate models to accurately determine which chemical reactions are dominant in the atmosphere. Consequently, experimental measurements that probe pH in atmospherically relevant particles are sorely needed to advance our understanding of aerosol acidity.This Account describes recent advances in measurements of aerosol particle acidity, specifically three distinct methods we developed for experimentally determining particle pH. Our acid-conjugate base method uses Raman microspectroscopy to probe an acid (e.g., HSO4-) and its conjugate base (e.g., SO42-) in individual micrometer-sized particles. Our second approach is a field-deployable colorimetric method based on pH indicators (e.g., thymol blue) and cell phone imaging to provide a simple, low-cost approach to ensemble average (or bulk) pH for particles in distinct size ranges down to a few hundred nanometers in diameter. In our third method, we monitor acid-catalyzed polymer degradation of a thin film (∼23 nm) of poly(ε-caprolactone) (PCL) on silicon by individual particles with atomic force microscopy (AFM) after inertially impacting particles of different pH. These measurements are improving our understanding of aerosol pH from a fundamental physical chemistry perspective and have led to initial atmospheric measurements. The impact of aerosol pH on key atmospheric processes, such as secondary organic aerosol (SOA) formation, is discussed. Some unique findings, such as an unexpected size dependence to aerosol pH and kinetic limitations, illustrate that particles are not always in thermodynamic equilibrium with the surrounding gas. The implications of our limited, but improving, understanding of the fundamental chemical concept of pH in the atmospheric aerosol are critical for connecting chemistry and climate.