Two types of the biological macromolecules poly(R-3-hydroxyalkanoates) have been identified: the high-molecular-weight microbial storage material (sPHA) and a short-chain variety, consisting of butyrate and valerate residues, complexed with other biomacromolecules such as calcium polyphosphate or proteins (cPHB/PHV). While sPHA has attracted, and still enjoys, a lot of attention from numerous scientists around the world, research on cPHB and the structurally and functionally related polymalate (PMA) is still in its infancy. In this article, we present a review on the chemical synthesis, structure, function and interactions of monodisperse cPHAs, the oligo(3-hydroxyalkanoates), with emphasis on the butyrates (OHB); we report hitherto unpublished results on the enzymatic degradation of cPHB and PMA, on a new analytical method for HB/HV detection in biological samples, and on OHB-mediated Ca 2+ transport through phospholipid bilayers of artificial vesicles; finally, we discuss possible mechanisms of ion transport through cell membranes, as caused by cPHB. The speculative—and provocative—question is asked whether the structurally simple PHAs may have evolved as storage materials and amphiphilic macromolecules before poly-peptides, -saccharides, and -nucleic acids, in the history of life, or under prebiotic conditions.