We report, to the best of our knowledge, the first demonstration of octave-spanning supercontinuum generation (SCG) on a silicon chip, spanning from the telecommunications c-band near 1.5 μm to the mid-infrared region beyond 3.6 μm. The SCG presented here is characterized by soliton fission and dispersive radiation across two zero group-velocity dispersion wavelengths. In addition, we numerically investigate the role of multiphoton absorption and free carriers, confirming that these nonlinear loss mechanisms are not detrimental to SCG in this regime. It is well known that pumping in the anomalous wavelength region near the zero group-velocity dispersion (ZGVD) wavelength may result in broadband SCG predominantly governed by soliton fission and dispersive wave generation [5]. Furthermore, it has been shown theoretically and experimentally that under suitable conditions, a second ZGVD wavelength on the opposite side of the pump will result in even broader SCG due to the generation of redshifted dispersive waves [3,4]. While silicon-based SCG in the MIR wavelength range has been previously demonstrated [11,12], the generated spectrum was limited to 990 nm, as the spectral broadening was mainly due to modulation instability with a single dispersive wave at lower wavelengths.In this Letter, we present a fundamentally different SCG, characterized by soliton fission and dispersive radiation across both ZGVD wavelengths, which enables us to achieve MIR spectra spanning 1.3 octaves, from 1.51 to 3.67 μm, in a silicon wire waveguide. This demonstration represents, to the best of our knowledge, the first octave-spanning SCG from a silicon chip.The silicon-on-insulator (SOI) waveguide used in our experiments has a cross section of 320 nm by 1210 nm, and a length of 2 cm, and is engineered to exhibit a ZGVD wavelength on each side of the 2.5 μm pump. Figure 1 shows the group-velocity dispersion (GVD) of the waveguide for the fundamental transverse electric (TE) mode, modeled using a custom finitedifference mode solver. The GVD is anomalous within the tuning range of the pump and falls to zero near 2.1 and 3.0 μm. The waveguide cross section and mode profile at λ 2.5 μm are shown in the inset. Fig. 1. Simulated group-velocity dispersion (GVD) curve for fundamental TE mode of an SOI waveguide with a cross section of 320 nm by 1210 nm, which results in anomalous GVD near the pump wavelength of 2.5 μm and zero-GVD wavelengths near 2.1 and 3.0 μm. The waveguide cross section and the mode profile are shown in the inset.