By hydrothermal reaction of CoCl2·6H2O with K2pcc (H2pcc = phenyl(carboxymethyl) phosphinic acid) at 423 K, a novel hybrid material of formula [Co2(pcc) 2(H2O)2]·H2O has been obtained. The compound, which is the first pcc/metal complex reported, exhibits a polymeric arrangement, where cobalt metal ions, linked together by bridging carboxylate and phosphinate oxygens, form infinite chains of edge-shared CoO6 octahedra. The cobalt chains are in turn linked together through important hydrogen-bonding interactions, which create an infinite 2D architecture. The two crystallographically independent cobalt centers, both displaying distorted octahedral coordination, present different environments as one is surrounded by six ligand oxygens and the other by four ligand oxygens and by two water oxygens. Careful magnetic studies performed by a home-built alternating currnet susceptometer reveal that the system undergoes an antiferromagnetic transition below 2.0 K leading to a canted structure. Field-dependent studies further indicate the occurrence of a metamagnetic transition at a critical field of 650 ± 50 G.