Polyester/Cotton blended fabrics are normally dyed by two-bath or one-bath two-step dyeing method. This paper deals with a new approach involving azeotropic ternary mixture of organic solvents pretreatment to dye polyester/cotton blends using disperse and reactive dyes in one-bath method. The effect of solvent pretreatments on dyeability, fastness, and few physicochemical properties has been investigated involving SEM, FTIR, DSC, and XRD studies, and results are presented.