Defoe's rocket (80) ensured a measure of revenge for last month's Euro 2012 defeat, though in truth neither side bore much resemblance to those on duty in Kiev.
Still, after Phil Jagielka's fine header (27) had cancelled out a similar effort from Daniele De Rossi (15), Defoe's winner at least sent England towards the road to Rio on the back of Hodgson's third straight friendly win.
The manager retains an unbeaten record over 90 minutes, too, while Defoe, Leighton Baines and John Ruddy, in particular, did their claims for more regular action no harm during a lively contest.
It took England a while to get going and De Rossi's opener - headed over Jack Butland after he had stolen a march on marker Michael Carrick - was deserved even as early as it came.
Matteo Destro might have doubled the lead before the visitors replied, Jagielka throwing himself at a Frank Lampard corner and steering his header across Salvatore Sirigu.
Chances came and went as regularly as substitutions after half-time, Ruddy keeping out Destro's sharp shot on the turn with almost his first touch and later denying Marco Verratti.
More to follow...
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