Ag-, Mg- and Mn-containing poly-p-xylylenes were obtained by solid-state photopolymerization of metal-p-xylylene mixtures at 77 K. Interaction of the metals with p-xylylene before and after its polymerization was studied using IR and UV-Vis spectroscopies. It was shown that Mg and Mn form strongly optically absorbing complexes with p-xylylene during codeposition, whereas Ag produces nanoclusters without chemical interaction with monomer and these clusters remain in the polymer matrix practically unchanged. Mg forms ionic complexes with a large contribution of covalent bonding. The p-xylylene in such complexes exists in the form close to its benzenoid one. During polymerization the complexes transform into sigma-bonded organomagnesium compounds incorporated within the polymer chains. Mn as a transition metal produces complexes of two types. Complexes of the first type are similar to those of Mg demonstrating similar behavior in course of polymerization, whereas those of the second type, formed by the interaction of d-orbitals of Mn with pi-orbitals of p-xylylene, are destroyed during polymerization.