This study evaluates the wrinkle behaviour and wrinkle resistant properties of cotton fabrics dyed by Direct Blue 2B in the presence and absence of nano-TiO2 particles. A finishing process on samples was performed before dyeing by means of 1,2,3,4-butanetetracarboxylic acid (BTCA) and sodium hypophosphite (SHP) using a pad dry cure method. Such experiments as wrinkle recovery test (AATCC-128), water drop test and dye fastness determination (ISO 105-C01) were conducted to understand how current treatment impacted the cotton fabrics’ properties. Finally, samples were characterised using the X-ray diffractometery method to scrutinise how crystallinity changes and dominates the structural parameter (wrinkle behaviour) of cotton fabrics. Furthermore, scanning electron microscopy (SEM) was used to visualise the surface variations of the samples before and after dyeing process. The results showed that the wrinkle resistant of cross-linked fabrics have been improved after direct dyeing. Furthermore, levelness dyeing and good fastness properties of dyes on cross-linked fabrics were observed.