Cross-linked poly(vinylene-arsine)s (4) were synthesized by a free-radical terpolymerization of phenylacetylene (2), hexaphenylcyclohexaarsine (l), and p- or m-diethynylbenzene (p- or m-3) at different compositions in the presence of a catalytic amount of AIBN. The number-average molecular weights of the resulting polymers were a few thousands estimated by gel permeation chromatography (GPC) analysis. By gas chromatography (GC) analysis p-3 was found to be more reactive during the polymerization than m-3 and the resulting cross-linked polymer (p-4) showed lower solubility than that of m-4. The cross-linked poly(vinylene-arsine)s showed higher glass transition temperature in the measurement of differential scanning calorimetry (DSC) and more red-shifted emission in chloroform solution than that of the linear poly(vinylene-arsine). These properties could be tuned by varying the monomer feed ratio.