Water exhibits rich polymorphism, where more than 20 crystalline phases have been experimentally reported. Five of them are metastable and form at low temperatures by either heating amorphous ice or degassing clathrate hydrates. However, such metastable phases rarely crystallise directly from liquid water, making it challenging to study metastable phase relations at relatively high temperatures. Here, we report that high-pressure metastable phases of ice, including two unknown phases named ices XXI and XXII, crystallise directly from liquid water in a deeply supercooled region around the homogeneous nucleation temperature. The key is to use emulsified water to stabilise supercooled water in laboratory timescales. Ices XXI and XXII are obtained by isothermal compression of emulsified water at 295 K and 250 K, respectively. Our powder x-ray and neutron diffraction analyses combined with molecular dynamics (MD) simulations revealed the surprisingly complex structures of these new phases with Z = 152 (ice XXI) and 304 (ice XXII). Ice XXI is topologically identical to 'ice T2' previously predicted by MD simulations, and our experimental structural model can be used as a benchmark for its structures in simulations, which depend on the force fields. On cooling, ice XXI transforms into an orientationally ordered counterpart named ice XXIII. Our results revealed the "hidden" structural complexity of water underlying the phase diagram, as implied by previous computational works. Further efforts at unveiling such metastable phase relations will bridge the large gaps between computational and experimental phase diagrams of water.