The aim of the current study was to present the clinical and radiological outcomes of monolithic zirconia superstructures compared to the metal–ceramic ones in the All-on-4 concept for the prosthetic rehabilitation of the maxillae. A total of 30 patients were subdivided into groups according to their superstructure type (metal–ceramic (n = 15) or monolithic zirconia (n = 15)). All implants were functionally loaded within 24 h after insertion with provisional acrylic superstructures. Prosthetic complications, marginal bone loss, plaque accumulation, probing pocket depth, bleeding on probing, and bite force were documented over a period of 5 years. Marginal bone loss around the implants of the ceramic group remained well over the five years (1.21 ± 0.23 mm). However, marginal bone loss was significantly lower around the implants in the monolithic zirconia group (0.22 ± 0.14 mm) (p < 0.001). Bleeding on probing, plaque accumulation, and probing pocket depth values were correlated with marginal bone loss. Among all evaluated parameters, no differences could be detected in terms of the angulation of the implants. Detachment or chipping was observed in seven cases in the metal–ceramic superstructure group. In all cases, dentures were removed and repaired in the laboratory. In the monolithic zirconia group, chipping was detected after one year in two cases, after two years in four cases, and after five years in one case and could be managed by polishing in situ. Monolithic zirconia superstructures presented superior results regarding the parameters evaluated.