The synergistic interaction between teammates in association football has properties that can be captured by Social Network Analysis (SNA). The analysis of networks formed by team players passing a ball in a match shows that team success is correlated with high network density and clustering coefficient, as well as with reduced network centralization. However, oversimplification needs to be avoided, as network metrics events associated with success should not be considered equally to those that are not. In the present study, we investigated whether network density, clustering coefficient and centralization can predict successful or unsuccessful team performance. We analyzed 12 games of the Group Stage of UEFA Champions League 2015/2016 Group C by using public records from TV broadcasts. Notational analyses were performed to categorize attacking sequences as successful or unsuccessful, and to collect data on the ball-passing networks. The network metrics were then computed. A hierarchical logistic-regression model was used to predict the successfulness of the offensive plays from network density, clustering coefficient and centralization, after controlling for the effect of total passes on successfulness of offensive plays. Results confirmed the independent effect of network metrics. Density, but not clustering coefficient or centralization, was a significant predictor of the successfulness of offensive plays. We found a negative relation between density and successfulness of offensive plays. However, reduced density was associated with a higher number of offensive plays, albeit mostly unsuccessful. Conversely, high density was associated with a lower number of successful offensive plays (SOPs), but also with overall fewer offensive plays and “ball possession losses” before the attacking team entered the finishing zone. Independent SNA of team performance is important to minimize the limitations of oversimplifying effective team synergies.