New iron(II) three-dimensional coordination polymer (3D CP), [Fe(µ3-Hcpna)2 ]n (1), was assembled under hydrothermal conditions from 5-(4’-carboxyphenoxy)nicotinic acid (H2 cpna) as a trifunctional organic N,O-building block. This stable microcrystalline CP was characterized by standard methods for coordination compounds in the solid state (infrared spectroscopy, elemental analysis, thermogravimetric analysis, powder and single-crystal X-ray diffraction). Structure and topology of 1 were examined and permitted an identification of a 3,6-connected framework of the rtl topological type. In addition, compound 1 acts as effective catalyst precursor for oxidative functionalization of alkanes (propane and cyclic C5 −C8 alkanes) under homogeneous catalysis conditions, namely for the oxidation of saturated hydrocarbons with H2 O2/H+ system to produce ketones and alcohols, and for alkane carboxylation with CO/H2 O/S2 O8 2− system to obtain carboxylic acids. The influence of an acid promoter and substrate scope (propane and cyclic C5 −C8 alkanes) were investigated. © 2019 by the authors. Licensee MDPI, Basel, Switzerland.