Natural biopolymers, which are renewable, widely available, biodegradable, and biocompatible, have attracted huge interest in the development of biocomposite materials. Herein, formulation–property relationships for starch/agar composite films were investigated. First, rapid visco analysis was used to confirm the conditions needed for their gelation and to prepare filmogenic solutions. All the original crystalline and/or lamellar structures of starch and agar were destroyed, and films with cohesive and compact structures were formed, as shown by SEM, XRD, and SAXS. All the plasticized films were predominantly amorphous, and the polymorphs of the composite films were closer to that of the agar-only film. FTIR results suggest that the incorporation of agar restricted starch chain interaction and rearrangement. The addition of agar to starch increased both tensile strength and elongation at break, but the improvements were insignificant after the agar content was over 50 wt.%. Contact angle results indicate that compared with the other samples, the 4:6 (wt./wt.) starch/agar film was less hydrophilic. Thus, this work shows that agar dominates the structure and properties of starch/agar composites, and the best properties can be obtained with a certain starch/agar ratio. Such composite polysaccharide films with tailored mechanical properties and surface hydrophilicity could be useful in biodegradable packaging and biomedical applications (wound dressing and tissue scaffolding).