A process for the preparation of a benzodithiophene compound having general formula: wherein: - A, B, C, D, E and F, each independently, represent a sulfur atom; or a group C-R 3 wherein R 3 represents: a hydrogen atom, a linear or branched C 1 -C 20 alkyl group, a cycloalkyl group optionally substituted, an aryl group optionally substituted, a heteroaryl group optionally substituted, a linear or branched C 1 -C 20 alkoxyl group, a group -CHO, a carboxyl group -COOR 4 wherein R 4 represents a linear or branched C 1 -C 20 alkyl group, an amide group -CONHR 4 or -CON(R 4) 2 wherein R 4 has the meanings indicated above; with the proviso that: - one of A, B and C and one of D, E, and F, represents a sulfur atom; - E represents a sulfur atom only in the case in which B represents a sulfur atom; - when E and B represent a sulfur atom, D represents a group C-R 3 described above, wherein R 3 is different from hydrogen; - the sum of the double carbon-carbon bonds (C=C) present in the two thiophene rings and in the benzene ring is equal to 5; - R 1 and R 2 each independently represent a hydrogen atom, a linear or branched C 1 -C 20 alkyl group, a cycloalkyl group optionally substituted, an aryl group optionally substituted, a heteroaryl group optionally substituted; said process comprising reacting at least one monohalogenated dithiophene compound having general formula: wherein X represents a halogen atom selected from chlorine, bromine, iodine, A, B, C, D, E and F have the same meanings described above: with at least one internal alkyne having general formula: wherein R 1 and R 2 have the same meanings defined above. - A, B, C, D, E and F, each independently, represent a sulfur atom; or a group C-R 3 wherein R 3 represents: a hydrogen atom, a linear or branched C 1 -C 20 alkyl group, a cycloalkyl group optionally substituted, an aryl group optionally substituted, a heteroaryl group optionally substituted, a linear or branched C 1 -C 20 alkoxyl group, a group -CHO, a carboxyl group -COOR 4 wherein R 4 represents a linear or branched C 1 -C 20 alkyl group, an amide group -CONHR 4 or -CON(R 4) 2 wherein R 4 has the meanings indicated above; with the proviso that: - one of A, B and C and one of D, E, and F, represents a sulfur atom; - E represents a sulfur atom only in the case in which B represents a sulfur atom; - when E and B represent a sulfur atom, D represents a group C-R 3 described above, wherein R 3 is different from hydrogen; - the sum of the double carbon-carbon bonds (C=C) present in the two thiophene rings and in the benzene ring is equal to 5; - R 1 and R 2 each independently represent a hydrogen atom, a linear or branched C 1 -C 20 alkyl group, a cycloalkyl group optionally substituted, an aryl group optionally substituted, a heteroaryl group optionally substituted; - one of A, B and C and one of D, E, and F, represents a sulfur atom; - E represents a sulfur atom only in the case in which B represents a sulfur atom; - when E and B represent a sulfur atom, D represents a group C-R 3 described above, wherein R 3 is different from hydrogen; - the sum of the double carbon-carbon bonds (C=C) present in the two thiophene rings and in the benzene ring is equal to 5; - R 1 and R 2 each independently represent a hydrogen atom, a linear or branched C 1 -C 20 alkyl group, a cycloalkyl group optionally substituted, an aryl group optionally substituted, a heteroaryl group optionally substituted; with at least one internal alkyne having general formula: wherein R 1 and R 2 have the same meanings defined above.