A microwave assisted sample introduction system based on the use of a TM010 cavity (MWDS2) has been employed for the introduction of 10% w/w organic solvent solutions in inductively coupled plasma atomic emission spectrometry (ICP-AES). Ethanol, propan-2-ol, formic and acetic acids have been used. Firstly, the effect of the incident microwave power and the sample uptake rate on the emission signal was evaluated. For all matrices tested, the higher emission signals were obtained when operating at the highest microwave power (i.e., 290 W) and sample uptake rate (400 μL min−1). Results with the MWDS2 were compared with those afforded by a desolvation system based on the use of a domestic microwave oven (MWDS) and by a conventional sample introduction system (CS). The MWDS2 provides the highest emission signals (up to 7 and 17 times higher than those with the MWDS and the CS, respectively). As regards the matrix effects originated by the organic solutions, results demonstrate that the use of a microwave-based sample introduction system, mainly the MWDS2, affords a noticeable reduction in the matrix effects originated by the use of organic solvent solutions in ICP-AES with a conventional sample introduction system. This behaviour can be explained by taking into account the solution transport rates afforded by the different sample introduction systems. For all the analytical lines and matrices tested and operating at 400 μL min−1, the MWDS2 gives rise to signal values that are, on average, 1.2 ± 0.2 times the signal obtained with water. For the MWDS and the CS, this factor takes values of 1.6 ± 0.2 and 2.0 ± 0.5, respectively. Transient matrix effects have been observed operating with the MWDS2 when switching between water and an organic matrix solution. These transient effects result in a drift time about 4.5 times higher than those with a CS.