An overview is provided on the possibilities of producing positively and negatively charged poly(beta-hydroxyalkanoates), PHAs. A large variety of bacterial polyesters with functionalized terminal side chains can be produced in microbial fermentation processes by a direct polymerization of respective carbon sources, that is, carbon sources that carry functional groups in their omega-position. However, charged PHAs are not accessible by a direct approach and must be synthesized via polymer-analogous reactions of functionalized bacterial polyesters. PHA polyanions are produced by converting the terminal functional groups into carboxylate groups, while PHA polycations are produced by introducing terminal amino groups. PHAs with terminal vinyl groups emerged as most suitable PHA precursors, as they can be produced in relatively high yields and the double bonds are sufficiently reactive. The oxidation of vinyl groups yields PHA polyanions. The conversion of terminal vinyl groups into epoxides with a subsequent ring-opening reaction with an amine yields PHA polycations. Other functionalized PHA that potentially lend themselves to polymer-analogous reactions are reviewed.