Exploration of new infrared (IR) nonlinear optical (NLO) materials is still in urgency owing to the indispensable roles in optoelectronic devices, resource exploration, and long-distance laser communication. The formidable challenge is to balance the contradiction between wide band gaps and large second harmonic generation (SHG) effects in IR NLO materials. In the present work, we proposed new kinds of NLO active units, d(0) transition metal fluorooxo-functional groups for designing mid-IR NLO materials. By studying a series of d(0) transition metal oxyfluorides (TMOFs), the influences of fluorooxo-functional groups with different d(0) configuration cations on the band gap and SHG responses were explored. The results reveal that the fluorooxo-functional groups with different d(0) configuration cations can enlarge band gaps in mid-IR NLO materials. The first-principles calculations demonstrate that the nine alkali/alkaline earth metals d(0) TMOFs exhibit wide band gaps (all the band gaps > 3.0 eV), large birefringence Delta n (> 0.07), and two W/Mo TMOFs also exhibit large SHG responses. Moreover, by comparing with other fluorooxo-functional groups, it is found that introducing fluorine into building units is an effective way to enhance optical performance. These d(0) TMOFs with superior fluorooxo-functional groups represent a new exploration family of the mid-IR region, which sheds light on the design of mid-IR NLO materials possessing large band gap.