This study aimed to investigate the interactions between insoluble fractions of different coffee infusions and major cocoa free antioxidants, catechin and epicatechin, as well as the interactions between different coffee infusions and dark chocolate. Espresso, filtered coffee, French press and Turkish coffee were used for this purpose. Antioxidant capacity (AC) measurements were performed by monitoring the percentage inhibition of 2,2-Diphenyl-1-picrylhydrazil (DPPH) radical. Multivariate approach was adopted for experimental design and data analysis steps. In dry basis, the AC values of infusions (mmol Trolox/kg) were ranged between 953 +/- 2.6 and 1184 +/- 11.3, while the AC values for their insoluble fractions were ranged between 45 +/- 0.0 and 105-1.3. Interactions between the insoluble fractions of coffee infusions and catechins were synergistic for espresso and additive/antagonistic for the other infusions. Interactions between coffee infusions and chocolate were synergistic for French press and Turkish coffee and additive/antagonistic for the other infusions.