Paul Massara said the actual unit prices of gas and electricity in the UK are among the lowest in Europe, but bills were high "because British houses waste so much energy".
In the supplier's second "Energy Explained" report, Mr Massara said: "If we can increase the efficiency of the UK's old and draughty housing, we can ensure that annual energy bills are some of the lowest too."
The npower chief executive warned consumers that the cost of bills was set to increase unless households introduce efficiency measures.
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Figures suggest that more than 11 million homes, or 42%, are in credit to their energy company.