The formation of a rigid porous biopolymer scaffold from aqueous samples of 1% w/v (suspension) and 5% w/v (gel) corn starch was studied using optical and nuclear magnetic resonance (NMR) techniques. The drying process of these systems was observed using a single-sided NMR scanner by application of the Carr–Purcell–Meiboom–Gill pulse sequence at diffrent layer positions. The echo decays were analyzed and spin–spin relaxation times (T2) were obtained for each layer. From the depth dependent T2 relaxation time study, it was found that the molecular mobility of water within the forming porous matrix of these two samples varied notably at diffrent stages of film formation. At an intermediate stage, a gradual decrease in mobility of the emulsion sample towards the air–sample interface was observed, while the gel sample remained homogeneous all along the sample height. At a later stage of drying, heterogeneity in the molecular dynamics was observed in both samples showing low mobility at the bottom part of the sample. A wide-angle X-ray diffraction study confirmed that the structural heterogeneity persisted in the final film obtained from the 5% corn starch aqueous sample, whereas the film obtained from the 1% corn starch in water was structurally homogeneous.