The garment industry demands stamping processes that are increasingly more agile and less damaging to the environment. In this scenario, digital printing, with the sublimation transfer printing technique, presents itself as a viable option for synthetic textile substrates. Among the synthetic fibres, polyamide (P.A.) fibres stand out, as they are light, soft, durable, and boast moderate sweat absorption; however, before sublimation, superficial treatment is necessary in order to present good results such as withstanding washing and maintaining colour intensity. This study addresses the surface modification of the PA6.6 textile substrate by activating non-thermal plasma at atmospheric pressure to receive dye through the sublimation method with dispersed dye. The knitted PA6.6 fabric surface treatment was performed with plasma application at atmospheric pressure using air in the Plasmatreater AS400 equipment. The sublimation transfer effects were evaluated by wash fastness and colourimetric tests. To assess the wettability effect of the control and treated samples, a contact angle test was carried out on PA6.6 samples. Fourier transform infrared spectroscopy (FTIR) proved the changes in chemical functional groups in the fibres. The results showed a decrease in the contact angle of the textile surface, 4–5 grayscale results for colour change and transfer for washing, and an increase in colour strength. In the FTIR tests, there is an increase in the transmittance value of aromatic, carboxylic groups (C=O, 580 cm−1), amides (N=H, 1630 cm−1), and methyl groups (CH 1369 to 1463 cm−1) as well as the presence of new functional groups in the 3064 cm−1 and 2860 cm−1 bands. These conditions allowed sublimation in the knitted PA6.6 fabric and showed increased colour strength and good wash fastness.