Densities, partial molar volumes, and viscosities of aqueous solutions of betaine have been measured at 5, 10, 15, 20, 25, 30, 37, and 45 °C over the concentration range 0.05 to 5.0 mol⋅L−1. The partial molar volumes show that betaine exists partly as a monohydrate and partly in its anhydrous form. The proportion of the anhydrous form increases with increasing temperature. Also, an associated form of betaine appears in concentrated betaine solutions, possibly with water as a bridging group. The significance of the viscosity B-coefficient is discussed. The signs of B st, the increment of the viscosity B-coefficients arising from structural changes of water, are negative and the signs of dB/dT, the temperature derivative of B, are positive. These results show that betaine is a water structure breaker especially at lower temperatures, and this effect decreases to insignificance at higher temperatures. The ionization equilibria of betaine were investigated in aqueous 0.5 mol⋅L−1 and 1.0 mol⋅L−1 NaNO3 at 5, 15, 25, and 37 °C by a potentiometric method. Using the least-square computer program SUPERQUAD, the complex forms are deduced to be betanium BH, bis(betanium) BHB, and bis(betaine) B2 or bis(betaine)hydrate BH2OB.