The bodies of Mary Lawson and her husband Sean, a council environment chief, were found at their Warwickshire home early on Sunday.
Rt Revd Martyn Snow said: "Mary made a very significant contribution to the work of the Church across the diocese.
"I am shocked and deeply saddened by this news and my thoughts and prayers are with Mary and Sean's colleagues, family and friends."
As well as serving as Canon of Leicester Cathedral, Mrs Lawson was Director of Education for the Diocese of Leicester between 2010 and 2014.
Expressing its "great sadness" at her death, the diocese said the 63 year old "led the Diocesan Board of Education through many significant changes which impacted diocesan schools..."
One neighbour of the couple in Rugby was quoted by The Times as saying: "This is a close-knit community and they both did more than their fair share for it...
"I'm just heartbroken they have died. You couldn't wish for a better couple or met a nicer pair of people."
After leaving the diocese Mary became head of a primary school in Leicester but had recently suffered from ill health following a stroke in 2015.
Sean Lawson, 50, was head of Envronment and Public Realm at Rugby Borough Council.
Det Insp Matthew Pyatt from Warwickshire Police said: "We are not treating the incident as suspicious. The incident was contained to the property and we're not looking for anyone else... the case will be handed over to the coroner."