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Composite arrays of multi-wall carbon nanotubes (MWNTs) and silicon nanowires (SiNWs) are fabricated by means of the chemical vapour deposition method in porous anodic aluminium oxide (AAO) templates. The results of the scanning electron microscopy, high-resolution transmission electron microscopy, and transmission electron microscopy have shown that SiNWs are successful nested or filled in the hollow cavities of synthesized MWNT arrays in AAO templates to form MWNT-SiNW composite arrays. The photoluminescence (PL) intensity degradation and a blueshift of PL peak position, usually created from the chemical instability of the SiNW surfaces, are decreased and eliminated clearly in the composite arrays. The composite arrays of MWNTs-SiNWs exhibit more enhanced intensity and stability of PL performance than the SiNW arrays deposited in AAO templates.