As the deepest group-V donor in Si, Bi has by far the largest hyperfine interaction and also a large I = 9/2 nuclear spin. At zero field this splits the donor ground state into states having total spin 5 and 4, which are fully resolved in the photoluminescence spectrum of Bi donor bound excitons. Under a magnetic field, the 60 expected allowed transitions cannot be individually resolved, but the effects of the nuclear spin distribution, −9/2 ≤ Iz ≤ 9/2, are clearly observed. A strong hyperpolarization of the nuclear spin towards Iz = −9/2 is observed to result from the nonresonant optical excitation. This is very similar to the recently reported optical hyperpolarization of P donors observed by EPR at higher magnetic fields. We introduce a new model to explain this effect, and predict that it may be very fast.PACS numbers: 78.55. Ap, Recent proposals [1][2][3][4][5] to use the electron and nuclear spins of shallow donor impurities as qubits for Si-based quantum computing (QC) have led to renewed interest in these systems [5][6][7][8][9][10][11]. Most studies have focused on 31 P, the most common donor in Si, with an I = 1/2 nuclear spin. Most QC schemes involve enriched 28 Si, as this eliminates the 29 Si nuclear spin, but the removal of inhomogeneous isotope broadening [6] also enables an optical measurement of the donor electron and nuclear spin using the donor bound exciton (D 0 X) transition [7], and furthermore allows for the hyperpolarization of both spin systems at very low magnetic fields by resonant optical pumping [10]. McCamey et al. [9] have reported a different effect in which P nuclear hyperpolarization can be achieved with nonresonant optical excitation in natural Si at high magnetic field and low temperature.Bismuth is the deepest group-V donor in Si, with a binding energy of 70.98 meV [12], and is monoisotopic ( 209 Bi), with a large I = 9/2 nuclear spin and a hyperfine interaction of 1475.4 MHz, more than 12 times the 117.53 MHz value for 31 P [13]. While invoked in some QC proposals [4], Bi has not been the subject of recent study. It is interesting to note that the Bi D 0 X in Si is described in the earliest studies of bound excitons (BE) in semiconductors [14,15] but has received little attention since then [16]. This likely resulted from the scarcity of samples and, until now, their low quality.Recently [17], Si:Bi samples have been grown from ultrapure natural Si ( nat Si) using a floating-zone technique, for applications involving far-infrared lasers [18]. Samples from those same crystals are studied here, and show very reproducible D 0 X no-phonon (NP) photoluminescence (PL) structure over a wide range of Bi concentration. The spectra shown here are from a slice having a resistivity of 5.5 Ω·cm, mostly due to Bi, since the residual B and P concentrations are estimated to be at least an order of magnitude less than the Bi concentration. The sample was mounted without strain in a high homogeneity (0.01 %) split pair superconducting magnet dewar in Voigt configuration, with magnetic field ...