As the global surfactant market continues to expand, there is an increasing need to develop bio‐based alternatives in the shift towards a circular economy. This study focuses on the synthesis of polar, amphoteric, amine‐oxide surfactants starting from biomass‐derived monosaccharides and demonstrating their potential in various applications. The synthesis involved a reductive amination of the sugars with an alkylamine and formaldehyde followed by oxidation to produce N‐oxide surfactants. These bio‐based surfactants exhibited promising properties, including high solubility, foamability, surface tension reduction, and critical micelle concentration. In particular, N‐GalA1.10 and N‐GalA1.12 showed comparable performance to commercial surfactants. Furthermore, these bio‐based surfactants demonstrated significantly lower skin irritation potential when compared to petrochemical‐derived counterparts like sodium laureth sulfate (SLES), making them potentially suitable for personal care products. The biodegradability assessment revealed that N‐GalA1.12 exhibited good biodegradation, indicating its potential environmental compatibility. In conclusion, this study highlights the potential of bio‐based N‐oxide surfactants derived from monosaccharides as sustainable and skin‐friendly alternatives to traditional amphoteric surfactants, like cocamidopropyl betaine (CAPB)