Core Ideas Water retention data from saturation to oven dryness were collected for a Vertisol. New water retention and differential water capacity models were developed. Draining of intra‐aggregate pore space triggers the dry field soil moisture state. Mode of the textural pore space controls shift to wet field soil moisture state. Vertisols are well suited for rainfed agriculture in water‐limited environments as a result of their unique water transfer and retention characteristics. Despite their importance, the agro‐hydrological behavior of these soils under seasonally dry climates is not yet fully understood. We collected water retention data for a Vertisol, measured from saturation to oven dryness on 27 undisturbed topsoil (0–0.05 m) samples from an experimental field in south‐central Spain and related this information to the occurrence of field‐observed preferential soil moisture states. A continuous function was fitted to the mean gravimetric water retention data, Θ, consisting of the sum of a double exponential model and the Groenevelt and Grant model. An inflection point at pressure head |h| = 1.1 × 105 cm, Θ = 0.12 kg kg−1, and an equivalent pore radius, δ = 14 nm, was interpreted as the boundary between the clay inter‐ and intra‐aggregate pore spaces, corresponding with the transition from the intermediate to the dry field soil moisture state. The mode of the textural pore space (|h| = 7.3 × 103 cm, Θ = 0.21 kg kg−1, and δ = 200 nm) matched the transition from the wet to the intermediate field soil moisture state. We related these characteristics of the soil water retention curve with the spatiotemporal soil moisture dynamics and patterns observed in the field, characterized by fast transitions between preferential soil moisture states. The proposed framework is suitable for comparing the effects of different soil management strategies on the agro‐hydrological performance of Vertisols.