Born Ralph Neville, he was the eldest son of the Very Revd and Hon George Neville-Grenville (Dean of Windsor and son of Richard Griffin, 2nd Baron Braybrooke) and his wife Lady Charlotte Neville-Grenville (née Lady Charlotte Legge, second daughter of George Legge, 3rd Earl of Dartmouth).
[4] He served in the British Army and was lieutenant-colonel of the West Somerset Yeomanry Cavalry.
[2] Neville-Grenville entered the British House of Commons as Member of Parliament (MP) for Windsor in 1841, representing it until 1847.
[6] He was appointed High Sheriff of Somerset in 1862 and was a deputy lieutenant and justice of the peace for the same county.
[2] On 18 September 1845, he married Julia Roberta Russell, daughter of Sir Robert Frankland Russell, 7th Baronet at All Souls Church, Langham Place.