In this work, we investigated the dependence of spin Seebeck effect (SSE) voltages on the thickness of yttrium iron garnet (Y3Fe5O12-YIG) thin films grown on a silicon (Si) substrate fabricated by a metal-organic decomposition (MOD) method. The thickness of films was controlled by repeated spin coating and annealing cycles. Based on grazing incidence X-ray diffraction measurements, the YIG thin films displayed high crystallinity without secondary peaks, despite the increase in thickness. Scanning electron microscopy revealed uniform, highly dense films for samples having a thickness in the range of 37–260 nm. Magnetic hysteresis loops showed similar coercivities of <36 Oe for all samples, confirming the high quality of the YIG films, regardless of mismatch between the lattice constants of YIG and the substrate. Spin Seebeck resistivity results revealed a strong dependence on the thickness of the samples and the local maxima for 138-nm-thick YIG. This was attributed to the effect of the magnon energy relaxation length (ξL), which is shorter in comparison to that of a single-crystal YIG film grown on gadolinium gallium garnet. In this study, facile fabrication of hundreds of nanometers-thick YIG films on a Si substrate was achieved, for applications involving thermoelectric energy harvesting.