An entirely new method to fabricate optically active and carrier-mediated excitable erbium complexes on silicon is presented. The Er-Si-O nano-complexes are formed by spin-coating a Si (100) substrate with an ErC13 solution, followed by a rapid thermal oxidation and annealing sequence (RTOA). Intense room-temperature luminescence is observed from the Er-Si-O nano-complexes, with a line width as narrow as 4 meV at room temperature. The Er emission at 1.53 μm can be excited both directly and through photo carriers. Formation and optical activation of the Er-Si-O nano-complexes are discussed. In addition, an application of the wet chemical synthesis technique to incorporation of the Er-Si-O nano-complexes into nano-porous silicon waveguides is demonstrated.