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We report an optical spectroscopy study on the single crystal of NaTiAsO, a sister compound of superconductor BaTiSbO. The study reveals unexpectedly two density wave phase transitions. The first transition at 320 K results in the formation of a large energy gap and removes most part of the Fermi surfaces. But the compound remains metallic with residual itinerant carriers. Below 42 K, another density wave phase transition with smaller energy gap scale occurs and drives the compound into semiconducting ground state. These experiments thus enable us to shed light on the complex electronic structure in the titanium oxypnictides.

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