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Most pharmaceutical excipients serve as binding agents in tablet formation. As an inactive pharmaceutical ingredient, an excipient should not interfere with the drug absorption into the body. Synthetic materials, such as polyethylene glycol (PEG), are well-known for their binding attributes in drugs. However, synthetic binders have become more complex in recent years which have resulted in higher levels of toxicity and a reduced solubility of the active pharmaceutical ingredient (API). Due to these factors, researchers are investigating inert, natural binding materials such as monosaccharides and polysaccharides. This research sought to investigate the effect of replacing PEG as an excipient in paracetamol tablets with monosaccharides: d-allulose and d-sorbitol; and polysaccharides: tamarind gum, pectin, guar gum, and xanthan gum. The tablets were formed using a binder dropping method into a 3D printed tablet mold. Analysis reviewed the effect of excipient selection on the crystal structure of the tablet using XRD, effect on thermal properties using DSC, and effect on the chemical structure using FTIR. Overall, excipient selection resulted in no significant changes in the APAP crystal structure which would signal the formation of a different compound. FTIR analysis showed that polysaccharide excipients do not affect the structure of APAP, while the sweeteners interacted with the -OH functional group. The synthetic excipient, PEG, had the greatest effect on the structure of APAP and was the only excipient producing new functional group peaks. All excipients reduced the maximum melting temperature of the APAP tablet with the polysaccharides having the smallest change. D-sorbitol provided the highest reduction in melting peak and onset temperatures.