Alkoxide-based solutions with compositions in the Pb[(Mg1/3Nb2/3)1-x Tix]O3 (PMNT) and Pb[(Zn1/3Nb2/3)1-x Tix]O3 (PZNT) systems were synthesized and used for the integration of thin layer dielectrics on platinized Si. A multilayering spin-casting method was used with rapid thermal processing of individual layers. Thin layers of each composition could be formed into a nonferroelectric pyrochlore phase or a ferroelectric perovskite phase depending upon processing conditions. Compositions containing greater amounts of PMN or PZN required higher processing temperatures for perovskite formation. The effects of composition and thermal processing conditions on the development and structure of crystalline phases, and dielectric properties, are reported.