Nitrogen ion was implanted into the nano-TiO2 film surfaces by electron cyclotron resonance (ECR) plasma modification to improve the optical reactivity in visible-light region for nano-TiO2. Diagnosing the N2 plasma by optical emission spectroscopy (OES) was applied to the process of plasma modification. X-ray photoelectron spectroscopy (XPS) was used for analysis of the binding of element after plasma modification. It is shown that the surface modification was caused by excitated N. The injecting of N2 and N2+ leads to the increase in the dissociative interstitial state N in the films. The doped N makes for TiO2-xNx appearing in the TiO2films. TiO2-xNx forms the impurity energy state in the TiO2 energy band gap and reduces the energy band gap. This is the main reason leading to the red shift of absorption edge.