An efficient method for the synthesis of triarylmethanes and difurylarylmethanes through solventless reactions between aldehydes and arenes in the presence of H3PW12O40 as a reusable catalyst under thermal and microwave irradiation conditions has been developed. H3PW12O40‐catalysed one‐pot consecutive Friedel–Crafts reactions between veratrole and aldehydes were also applied as a convenient protocol for the preparation of symmetrical 9,10‐diaryl‐2,3,6,7‐tetramethoxyanthracenes. The conversion of aldehydes into their corresponding acylals in the presence of H3PW12O40 and the one‐pot reactions of diveratrylmethanes with these acylals were also used for the synthesis of symmetrical and unsymmetrical 9,10‐diaryl‐2,3,6,7‐tetramethoxyanthracenes.