The cloudiness of hydrogen-bonded LBL films assembled from polyvinylpyrrolidone (PVPON) and poly(acrylic acid) (PAA) is studied in detail by two approaches: spectroscopy (Fabry-Pérot fringes) and microscopy (AFM). Fabrication parameters such as temperature, molecular weight, pH value, and rinsing time, have notable influences on film cloudiness. The buildup of the PVPON/ PAA film is a two-stage process of adsorption and chain rearrangement. Generally, adsorption is fast, while chain rearrangement is slow. The fast adsorption process traps defects, whereas the relatively slow chain-rearrangement process can not heal the defects in time; therefore; the number of defects continuously increases as LBL assembly proceeds, and a cloudy, heterogeneous film is produced. However, the as-prepared cloudy films become transparent and homogeneous on subsequent annealing in acidic water. UV/Vis spectroscopy and fluid AFM were applied to monitor this transition ex situ and in situ, respectively. It is found that increasing the annealing temperature accelerates the transition from cloudy to transparent, and the transition of the film made from higher molecular weight polymer is slower.