Self-assembly of two complex salts [Cu(ida)(H2O)(2)], (ida(2-) = iminodiacetate) and K-4[M(CN)(8)]center dot 2H(2)O (M = Mo, W) resulted in the unique examples of 2-D layer K-4{[Cu(ida)](2)[M(CN)(8)]}center dot 4H(2)O coordination polymers, where M = Mo (1) and W (2). These two assemblies are rare instances of d-block metal complexes with imino or amino acids and polycyanidometallates. Furthermore, both complexes in their ground states are paramagnetic materials with weak antiferromagnetic interactions at low temperature. Interestingly, photoirradiation of both systems at 10 K with a 407 nm light for 24 h results in the photomagnetic effect observed as a 30% and 3% increase of magnetization for 1 and 2, respectively, which relax to the initial ground state after heating above 200 K. To the best of our knowledge, this is the first report of the photomagnetic effect for a Cu(II)-W(IV) system.