Free phytosterols (FPS) have been utilized in recent research compared to their esterified or soluble counterparts in order to reduce costs and inconvenience associated with esterified phytosterols during processing. Furthermore, bans on trans fats have led to the need for substitutes that can mimic their desirable properties. This research focuses on the analysis of FPS co-crystallized with fully hydrogenated soybean oil (FHSO) and soybean oil (SO) as a zero-trans substitute for puff pastry shortening and various other types of shortenings. Differential interference contrast microscopy and wide angle x-ray diffraction demonstrated co-crystallization of FPS with FHSO and SO. Polymorphic forms were characterized as β' and β for all samples. The addition of FPS decreased oil loss (OL) and melting profiles of FPS samples were extended to higher temperatures compared to commercial puff pastry shortening. Rheological properties suggested FPS blends may be acceptable for bakery applications. With further research, FPS co-crystallized with FHSO and SO may be used as a suitable trans-fat free substitute for several types of shortening, including puff pastry shortening.