Artificial photosynthesis is broadly defined as the process of solar energy conversion into chemical fuels and represents a promising route towards alleviating the global energy crisis. In this context, the development of photocathodes for the use in photoelectrochemical cells is an attractive approach for the storage of solar energy in the form of a chemical energy carrier (e.g. H$\mathrm{<mrow\; data-mjx-texclass="ORD">2</mrow>}$ and CO$\mathrm{<mrow\; data-mjx-texclass="ORD">2</mrow>}$-reduction products from H$\mathrm{<mrow\; data-mjx-texclass="ORD">2</mrow>}$O and CO$\mathrm{<mrow\; data-mjx-texclass="ORD">2</mrow>}$). However, molecular catalyst-based photocathodes remain scarcely reported and typically suffer from low efficiencies and/or stabilities due to inadequate strategies for interfacing the molecular component with the light-harvesting material, with benchmark systems continuing to rely on precious metal components. In this thesis, the straightforward preparation of a p-silicon|mesoporous titania|molecular catalyst photocathode assembly that is active towards proton reduction in aqueous media is first established. The mesoporous TiO$\mathrm{<mrow\; data-mjx-texclass="ORD">2</mrow>}$ scaffold acts as an electron shuttle between the silicon and the catalyst, while also stabilising the silicon from passivation and enabling a high loading of molecular catalysts. When a Ni bis(diphosphine)-based catalyst is anchored on the surface of the electrode, a catalytic onset potential of +0.4 V vs. RHE and a high turnover number of 1 $\times$ 10$\mathrm{<mrow\; data-mjx-texclass="ORD">3</mrow>}$ was obtained from photoelectrolysis under UV-filtered simulated solar irradiation at 1 Sun after 24 hours. Notwithstanding its aptitude for molecular catalyst immobilisation, the Si|TiO$\mathrm{<mrow\; data-mjx-texclass="ORD">2</mrow>}$ photoelectrode showed great versatility towards different types of catalysts and pH conditions, highlighting the flexible platform it represents for many potential reductive catalysis transformations. The Si|TiO$\mathrm{<mrow\; data-mjx-texclass="ORD">2</mrow>}$ scaffold was extended towards solar CO$\mathrm{<mrow\; data-mjx-texclass="ORD">2</mrow>}$ reduction via the immobilisation of a novel phosphonated cobalt bis(terpyridine) catalyst to achieve the first precious metal-free, CO$\mathrm{<mrow\; data-mjx-texclass="ORD">2</mrow>}$-reducing molecular hybrid photocathode. Reducing CO$\mathrm{<mrow\; data-mjx-texclass="ORD">2</mrow>}$ in both organic-water and purely aqueous conditions, the activity of this photocathode was shown to be affected by its environment and reached record turnover numbers for CO production by a molecular photocathode under optimal conditions, maintaining stable activity for more than 24 hours. Critically, in-depth electrochemical and in situ resonance Raman and infrared spectroelectrochemical investigations provided key insights into the nature of the surface-bound Co complex under reducing conditions. While demonstrating the power and precision offered by such in situ spectroelectrochemical techniques, these studies ultimately alluded to a catalytic mechanism that contrasts with that reported for the in-solution (homogeneous) catalyst. Overall, this affords a distinct mechanistic pathway that unlocks an earlier catalytic onset and enables photoelectrochemical activity. Finally, in the context of improving product selectivity in molecular-based CO$\mathrm{<mrow\; data-mjx-texclass="ORD">2</mrow>}$ reduction, polymers based on the cobalt bis(terpyridine) motif were synthesised and immobilised on inverse opal-type electrodes designed specifically to accommodate large molecules. Rational design of the polymers’ co-monomers was aimed towards the provision of an artificial environment for the active complex that would influence product selectivity, which was ultimately demonstrated by the improvement of a H$\mathrm{<mrow\; data-mjx-texclass="ORD">2</mrow>}$:CO product ratio of 1:2 (molecule) to 1:6 (polymer). Further studies of this all-in-one system included modulating its degree of cross-linkage as well as a CO$\mathrm{<mrow\; data-mjx-texclass="ORD">2</mrow>}$ reducing demonstration photocathode on a Si|inverse-opal TiO$\mathrm{<mrow\; data-mjx-texclass="ORD">2</mrow>}$ scaffold.