Porous Si (PS) was fabricated simply by electrochemical anodic etching of a Si wafer. By a combination of SEM, EDX and infrared spectrum measurements hydrogen-terminated crystalline Si surfaces were identified. Transparent Si nanocolloids were obtained via thermally-initiated hydrosilation of the hydrogenated Si surfaces reaction with unsaturated 1-undecene. In contrast to weak luminescence in the hydrogenated PS dispersed in toluene, intense luminescence was observed in the Si nanocolloid. In the Si nanocolloid, both strong luminescence and long-term stability can be correlated with alkylated passivation, as formation of Si–C bonds identified in infrared spectrum. Additionally, the oxidation effect was noticeable in affecting the luminescence of nano-Si during the process.