Over one billion people lack access to electricity and many of them in rural areas far from existing infrastructure. Off-grid systems can provide an alternative to extending the grid network and using renewable energy, for example solar photovoltaics (PV) and battery storage, can mitigate greenhouse gas emissions from electricity that would otherwise come from fossil fuel sources. This paper presents a model capable of comparing several mature and emerging PV technologies for rural electrification with diesel generation and grid extension for locations in India in terms of both the levelised cost and lifecycle emissions intensity of electricity. The levelised cost of used electricity, ranging from $0.46–1.20/kWh, and greenhouse gas emissions are highly dependent on the PV technology chosen, with battery storage contributing significantly to both metrics. The conditions under which PV and storage becomes more favourable than grid extension are calculated and hybrid systems of PV, storage and diesel generation are evaluated. Analysis of expected price evolutions suggest that the most cost-effective hybrid systems will be dominated by PV generation around 2018.