The aim of this retrospective study was to investigate the clinical performance of posterior complex resin composite (RC) and amalgam (AM) restorations after a five-year period. One hundred and nineteen complex Class II restorations placed by dental students were evaluated using the USPHS criteria. Data were analyzed using Chi-square, Mann–Whitney, and Wilcoxon tests at a 0.05 level of significance. After five years, the percentages of clinically satisfactory complex Class II RC and AM restorations were 78% and 76.8%, respectively. The main reasons for the failure of AM restorations included secondary caries (Bravo—10.1%), defective marginal adaptation (Charlie—8.7%), and fracture of the tooth (Bravo—7.2%). RC restorations presented failures related to the fracture of the restoration (Bravo—16%) and defective marginal adaptation (Charlie—8.2%). There was a significantly higher incidence of secondary caries for AM restorations (AM—10.1%; RC—0%; p = 0.0415) and a higher number of fractures for RC restorations (AM—4.3%; RC—16%; p = 0.05). Regarding anatomy, AM restorations presented a significantly higher number of Alfa scores (49.3%) compared to RC restorations (22.4%) (p = 0.0005). The results of the current study indicate that complex class II RC and AM restorations show a similar five year clinical performance.