Medium-chain-length poly-3-hydroxyalkanoates (mcl-PHAs) with varied monomeric compositions were biosynthesized by producer bacteria fed with different fatty acids as carbon source. Octanoic-, lauric-, stearic-, and oleic acids were used to produce four types of mcl-PHAs viz. PHA-OC, PHA-LA, PHA-ST, and PHA-OL, respectively. The mcl-PHAs as film-casted preparations exhibit distinct traits e.g., PHA-OC and PHA-ST films are less flexible than PHA-LA while PHA-OL is a sticky, glue-like material; PHA-ST is opaque whereas PHA-OC, PHA-LA, and PHA-OL displayed transparent layers. The observation is attributed to polymer chain packing and side chain crystallization. A structure-property investigation of these biopolymers was carried out employing different spectroscopic and microscopic analyses in addition to thermal analyses. Comparative analyses of the results were applied in the interpretation and discussion of structure-property relationship. [ABSTRACT FROM AUTHOR]