Synthetic soaps of N-lauroyl amino acid surfactants (LAAS) were synthesized in this work from lauroyl chloride and five typical amino acids with different α-substituents including α-alanine or α-aminobutyric acid with a hydrophobic α-substituent, serine with a hydrophilic α-substituent, and glutamic acid with an ionizable α-substituent normalized to Gly with the simplest α-amino acid structure to compare the α-substituent effect on physicochemical properties and application performance of LAAS. The surface adsorption, micellization, foamability, emulsification, wettability, and detergency of these LAAS were investigated. Experimental results indicate that the hydrophobic α-substituent of amino acid can reduce both critical micelle temperature and critical micelle concentration of LAAS, promote surface adsorption and general performance with respect to foamability, emulsifying power, and wetting power, while the hydrophilic α-substituent is on the contrary. Moreover, sodium lauroyl glycinate demonstrates the best overall detergency among five LAAS, and is the solely one performing better detergency than sodium laurate for all three standard soiled swatches, indicating the potential for detergents.