The combination of natural derived compounds glyceryl undecylenate, glyceryl caprylate and other glycols are skin friendly and they exhibited great antimicrobial activity. In current study, the antimicrobial activity of these nature derived compounds was evaluated against gram-positive, gram-negative bacterial and fungi after their combination with w/o and w/s formulations. Three types of ingredients (plant derived 1,3-propanediol, 1,3-butylene glycol and 1,2-pentanediol) were considered for blending to improve the antimicrobial effect along with stability in w/o and w/s formulation. In current investigation, it has been observed that the complex of glyceryl undecylenate and glyceryl caprylate and 1,2-pentanediol found be very stable, and it have provided excellent antimicrobial activity. Moreover, this complex showed superior antimicrobial activity and stability than the complex with 1,3 propanediol and 1,3-butanediol. Hence, the complex of natural combination with 1,2-pentanediol can be potential candidate as alternative preservative as well as high quality cosmetic ingredient.