Carlton Cole opened his England Under-21 account with a first-half double strike to give Peter Taylor the perfect start back in his role as coach.
Cole netted twice for England Under-21s
The Aston Villa striker pounced on a defensive error by Oleg Karamushka to fire home from close range after a fine right-wing cross from Jermaine Pennant.
Stewart Downing crossed from the left for Cole to convert his second.
Oleksander Aliyev pulled one back for Ukraine late on before Darren Bent scored from close range in injury time.
The scoreline may have flattered England, but given their impressive first-half display they deserved the win - largely inspired by the tenacious Pennant.
Taylor fielded a largely inexperienced side for his first game back in charge as England Under-21 coach.
But the team gelled immediately and produced some excellent, fluid football.
Arsenal winger Pennant was lively down the right and proved a constant threat to the Ukraine defence, who were run ragged in the opening stages.
James Milner took up some clever positions and moved the ball well from midfield to attack.
Indeed, it was Milner who had England's first good chance on goal when he picked up Nicky Hunt's defence-splitting pass before turning and rifling a shot just over the crossbar.
Jonathan Stead should have done better when set up by Pennant, but the unmarked Blackburn striker placed the ball just wide.
With the Ukraine defence completely at sea, it was only a matter of time before England scored and Cole was on hand to capitalise on another howler by the visitors.
Pennant pinged over an excellent cross from the right which Karamushka inexplicably cleared into the path of Cole, who blasted the ball home.
The goal momentarily stung Ukraine into action and Vorobey had two good chances, one of which forced Scott Carson to make a fine save.
Andrei Oberemko also flashed a free-kick over the crossbar, but in truth goalkeeper Carson had little to do as England finished the half as they had started - in the ascendancy.
Cole added his second of the evening just before the break when he turned in Downing's cross from the left at the second attempt after more defensive confusion which saw Karamushka immediately substituted.
The England goalscorer was replaced by Crewe's Dean Ashton after the interval and Bent was also introduced to the attack.
Ukraine raised their game and attacked the England defence, with the visitors' Dinamo Kiev contingent combining well.
Anton Ferdinand, brother of Manchester United's Rio, acquitted himself well at centre half in his first Under-21 appearance for England, who lost their way in the second half.
The hosts failed to wrestle the initiative away from Ukraine and they deservedly got a goal late on.
The lively Aliyev drilled a low shot past Carson after England failed to clear their lines.
Ukraine's goal took the shine off an otherwise impressive start to Taylor's return as coach, but Bent restored the two-goal cushion in injury time, converting Ashton's pass from four yards out.
England U21: Carson, Hunt (Hoyte 46), Richards (Harding 46),
Ferdinand, Kilgallon, Milner (Bent 59), Pennant, O'Neil,
Cole (Whittingham 46), Stead (Ashton 46),
Downing (Reo-Coker 76).
Subs Not Used: Lonergan, Davenport, Clare, Welsh, Tonge,
Westlake, Camp, Carter.
Goals: Cole 13, 42, Bent 90.
Ukraine U21: Shyriayev, Karamushka (Proshyn 44), Ischenko,
Cheberyachko, Yatsenko, Milevsky, Pivnenko,
Golaydo (Pukanych 46), Vorobey, Samborskyy, Oberemko.
Subs Not Used: Pyatov, Aliyev, Mykhalyk, Yarmash, Brovkin.
Goals: Aliyev 88.
Ref: Claude Colombo (France).