The photoproduct of octacyanomolybdate(IV) and -tungstate(IV) with ethylenediamine and triethylenetetramine give complexes of the type K3[Mo(O2)(O)(OH)(C9H7ON)]·3C9H7ON I, K2[W(O2)(O) (C9H7ON)3] II and K3[Mo(CN)3(OH)4(C9H7ON)]·2C9H7ON·3H2O III with 8-quinolinol (oxine). The IR spectra of the complex III shows the presence ofv(CN) peaks in the range 2047–2108 cm−1 and oxine groupv(C-O) in the complex I, II and III in the range of 1100–1150 cm−1. The lower region of IR spectra shows the M=O stretching while the higher thev(N-H) andv(OH). Thermal studies show the removal of uncoordinated water at 131‡C from complex III. The decomposition of complexes I and II start from 150 and 212‡C respectively. Oxine and cyano molecules were removed in stages at higher temperatures. The final product of the thermal decomposition was oxide which was of polymeric nature. The kinetic parameters viz. order of reaction ‘n’ and activation energy ‘E’ were determined by different methods.