Different sample preparation methods were evaluated for the simultaneous multielement analysis of wine samples by inductively coupled plasma optical emission spectrometry (ICP-OES) and inductively coupled plasma mass spectrometry (ICP-MS). Microwave-assisted digestion in closed vessel, thermal digestion in open reactor, and direct sample dilution were considered for the determination of Li, Be, Na, Mg, Al, K, Ca, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, As, Se, Sr, Y, Mo, Cd, Ba, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Tl, Pb, and Bi in 12 samples of red wine from Valencia and Utiel-Requena protected designation of origin. ICP-MS allows the determination of 17 elements in most of the samples, and using ICP-OES, a maximum of 15 elements were determined. On comparing the sample pretreatment methodology, it can be concluded that the three assayed procedures provide comparable results for the concentration of Li, Na, Mg, Al, K, Ca, Mn, Fe, Zn, and Sr by ICP-OES. Furthermore, ICP-MS data found for Cu, Pb, and Ba were comparable. Digestion treatment provides comparable values using both total decomposition in open system and microwave-assisted treatment for Cu by ICP-OES and for Cr, Ni, and Zn by ICP-MS. Open vessel total digestion provides excess values for Cr, Mn, Fe, and Zn by ICP-OES and defect values for Se. However, direct measurement of diluted wine samples provided uncomparable results with the digestion treatment for Mn, Cu, Pb, Zn, Ba, and Bi by ICP-OES and for Mg, Cr, Fe, Ni, and Zn by ICP-MS. Therefore, it can be concluded that microwave-assisted digestion is the pretreatment procedure of choice for elemental analysis of wine by ICP-based techniques.