This study evaluates the anthocyanins and derived pigments composition of Vitis Vinifera red wines of Vranec, Merlot and Cabernet Sauvignon, produced in 2006, 2007 and 2008 vintages from the Tikveš wine region in Republic of Macedonia. Their profile was established using matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF-MS) technique. A total of 22 anthocyanins and derived pigments have been identified in the samples including 10 anthocyanins, 1 ethyl-bridged flavanol-anthocyanin adduct and 11 pyranoanthocyanins. MALDI-TOF-MS analysis was performed after solid-phase extraction (SPE) of the wines using, for the first time, Zip-Tip C18 stationary phase, introducing a novel small-scale sample cleanup procedure prior to the rapid MALDI-TOF-MS fingerprinting of wine samples. 2',4',6'-trihydroxyacetophenone (dissolved in acetonitrile/water 1/1, V/V) was used as a matrix. The qualitative screening of anthocyanins and derived pigments with MALDI-TOF-MS confirmed the presence of glucoside, acetylglucoside and p-coumaroylglucoside derivatives of anthocyanins in the wine samples. Furthermore, pyranoanthocyanins formed by reactions of anthocyanins with pyruvic acid and acetaldehyde, as well as flavanol-pyranoanthocyanins and ethyl-bridged flavan-3-ol-anthocyanin adduct pigments have been detected in the samples.