Metallic photocathodes have drawn attention due to their outstanding performances of ultrafast photoelectric response and long operational lifetime. However, due to their high work function and the large number of scattering events, metallic photocathodes typically are driven by ultraviolet laser pulses and characterized by low intrinsic quantum efficiency (QE). In this work, a new type of Mie-type silver (Ag) nano-sphere resonant structure fabricated on an Ag/ITO composite substrate is used to enhance the photocathode QE, where Mie scattering resonance is used to enhance the local density of optical state and then to improve the light absorption and electron transporting efficiency in Ag nano-spheres. The cesium (Cs) activation layer is also used to lower the electron work function and then to excite photoemission in the visible waveband for Ag photocathode. The optical characteristics of Ag nano-sphere arrays are analyzed by using finite difference time domain method. For the investigated Ag nano-sphere array, theoretical results show that Mie-type electric dipole resonance modes can be obtained over the 400–600 nm waveband by adjusting the sphere diameter, and the large resonance-enhanced absorption can be achieved in nanospheres at the resonance wavelength. The Ag nano-spheres are fabricated on the Ag/ITO substrate by magnetron sputtering and annealing process, then the Cs activation layer is deposited on surface, and finally QE is measured in an ultra-high vacuum test apparatus. Experimental results show that over 0.35% of QE is obtained for Ag nano-sphere particle (with a diameter of 150 nm) at a wavelength of 425 nm, and the wavelength positions of QE maxima are in agreement with Mie resonance for corresponding geometry predicted from the computational model. Given these unique optoelectronic properties, Ag nanophotonic resonance structured photocathodes represent a very promising alternative to photocathodes with flat surfaces that are widely used in many applications today.