We have constructed a photoelectron imaging spectrometer with super-resolution image processing and have applied it to the photoionization of nitric oxide and benzene in molecular beams. A field programmable gate array is employed for real-time subpixel centroiding calculations on hardware, providing 64 megapixel resolution (8192 x 8192 pixels). We examined eight different centroiding algorithms based on the center-of-gravity (COG) and Gaussian fitting (Gauss) methods and have found that the two-dimensional COG (2D-COG) and weighted mean of Gaussian center (w-Gauss) methods have the best performance. The excellent performance of the instrument is demonstrated by visualizing a 25 mu m diameter pore structure of an MCP, indicating a spatial resolution of 0.03%. The photoelectron image in one-color (1 + 1) resonance-enhanced multiphoton ionization of nitric oxide using a nanosecond laser provided a photoelectron kinetic energy resolution of 0.2%. This resolution is Currently restricted by charged-particle optics. The photoelectron energy and angular distributions in the one-color (1 + 1) resonance-enhanced multiphoton ionization of benzene via 6(1) and 6(1) 1(1) vibronic levels in the S-1 state are also presented. The results demonstrate that photoelectron angular anisotropy varies with the photoelectron kinetic energy and the vibronic state of the cation.