Polymers exhibiting both antimicrobial and biodegradable properties are of great interest for next generation materials in healthcare. Among those, cationic polycarbonates are one of the most promising classes of materials because of their biodegradability, low toxicity, and biocompatibility. They are typically prepared by a chemical postmodification after the polymer has been synthesized. The main problem with the latter is the challenges of ensuring and verifying complete quaternization within the polymer structure. Herein, we report the first example of synthesizing and polymerizing charged aliphatic cyclic carbonates with three different alkane pendant groups (N-methyl, N-butyl, and N-hexyl) by ring-opening polymerization (ROP). These charged eight-membered cyclic carbonates displayed extraordinary reactivity and were even polymerizable in polar solvents (e.g., DMSO) and in catalyst free conditions that are generally unobtainable for other ring opening polymerization processes. A computational study was carried out and the findings were in agreement with the experimental data in regards to the dramatic increase in reactivity of the charged monomer over their neutral analogs. Furthermore, a series of hydrogels were prepared using the different charged eight-membered cyclic carbonates, and we found it to have a significant impact on the hydrogels' ability to swell and degrade in water. Finally, the hydrogels demonstrated antibacterial activity against Escherichia coli (Gram-negative) and Staphylococcus aureus (Gram-positive). These materials could be ideal candidates for biologically relevant applications where cationic structure is required.