This paper presents the structural features of ionic complexes formed by morpholine and metal ions which belong to group VA, namely Sb(III) and Bi(III). A series of target inorganic-organic hybrid compounds of the general formula [NH(2)(C(2)H(4))(2)O](2)MX(5) (where M = Sb, Bi; X = Cl, Br) has been synthesized by incorporating the organic component (morpholine) into the highly polarizable one-dimensional halogenoantimonate(III)/halogenobismuthate(III) chain network. Among the studied compounds, four were found to crystallize in the room temperature phase in the piezoelectric, orthorhombic space group P2(1)2(1)2(1), Z = 4, the feature being confirmed by the powder second harmonic generation of light and piezoelectric measurements. Dielectric dispersion studies between 200 Hz and 2 MHz disclosed a relaxation process below room temperature well described by the Cole-Cole equation. Based on crystal structures available in Cambridge Structural Database (version 5.32, November 2010) we attempt to show a relationship between the acentric symmetry of compounds and the type of anionic network within the R(2)MX(5)-subgroup (where R denotes organic cation) of halogenoantimonates(III) and halogenobismuthates(III).