We present a novel near-infrared spectroscopy technique based on Dual-Comb optical interrogation (DC-NIRS) applied to dispersive media. The technique recovers the frequency response of the medium under investigation by sampling its spectral response in amplitude and phase. The DC-NIRS reference and sample signals are generated using electro-optic modulation which offers a cost-effective, integrable solution while providing high adaptability to the interrogated medium. A careful choice of both line spacing and optical span of the frequency comb ensures that the retrieved information enables the reconstruction of the temporal impulse response of the medium, known as the diffuse-time-of-flight (DTOF), to obtain its optical properties with a 70 µs temporal resolution and 32 ps photon propagation delay resolution. Furthermore, the DC-NIRS technique also offers enhanced penetration due to noiseless optical amplification (interferometric detection). The presented technique was demonstrated on a static bio-mimetic phantom of known optical properties reproducing a typical brain’s optical response. The DTOF and optical properties of the phantom were measured, showing the capabilities of this new technique on the estimation of absolute optical properties with a deviation under 3%. Compared to current technologies, our DC-NIRS technique provides enhanced temporal resolution, spatial location capabilities, and penetration depth, with an integrable and configurable cost-effective architecture, paving the way to next-generation, non-invasive and portable systems for functional brain imaging, and brain-computer interfaces, among other. The system is patent pending PCT/ES2022/070176.