Conjugated poly(p-phenylene ethynylene) networks with interesting optoelectronic properties were synthesized by the palladium-catalyzed polycondensation of 2,5-diiodo-4-[(2-ethylhexyl)oxy]methoxybenzene, and 1,4-diethynyl-2,5-bis-(octyloxy)benzene, and 1,4-diethynyl-2,5-bis-(octyloxy)benzene, with 1,2,4-tribromo-benzene as cross-linker. The cross-linker concentration was varied and materials with different cross-link densities were prepared. The materials were processed into films by simultaneous polymerization and shaping. An alternative approach is to synthesize these cross-linked polymers in the form of spherical particles, which can be processed from dispersions.