We propose an all-laser processing approach allowing controlled growth of organic-inorganic superlattice structures of rare-earth ion doped tellurium-oxide-based glass and optically transparent polydimethyl siloxane (PDMS) polymer; the purpose of which is to illustrate the structural and thermal compatibility of chemically dissimilar materials at the nanometer scale. Superlattice films with interlayer thicknesses as low as 2 nm were grown using pulsed laser deposition (PLD) at low temperatures (100 °C). Planar waveguides were successfully patterned by femtosecond-laser micro-machining for light propagation and efficient Er(3+)-ion amplified spontaneous emission (ASE). The proposed approach to achieve polymer-glass integration will allow the fabrication of efficient and durable polymer optical amplifiers and lossless photonic devices. The all-laser processing approach, discussed further in this paper, permits the growth of films of a multitude of chemically complex and dissimilar materials for a range of optical, thermal, mechanical and biological functions, which otherwise are impossible to integrate via conventional materials processing techniques.