In this review, the relevance of the combined use of the microwave (MW) and phase transfer catalytic (PTC) techniques is studied within alkylations. In the solid–liquid phase C-alkylation of a series of simple CH-acidic compounds including P=O containing derivatives, in most cases there is no need to use a phase transfer catalyst, as MW promotes the reaction in itself. In the MW-assisted solid–liquid phase alkylation of phenol derivatives, the presence of an onium salt as a phase transfer catalyst ensures the predominance of the O-alkylation. In the absence of base and catalyst, the alkylation of phenol derivatives proved to be C-selective. As regards the MWpromoted solid–liquid phase alkylating esterification of phosphinic acids, the use of a phase transfer catalyst was beneficial in case of alkylating agents of normal reactivity. In MW-assisted N-alkylations there is no general rule for the relevance of a phase transfer catalyst. In the alkylation of phenotiazine, the presence of an onium salt promotes the formation of the N-alkylated product, while in the absence of catalyst, the C-alkylation is predominant. Most of the C- and O-alkylations was performed under solvent-free conditions.