The Blues were ruthlessly punished by Alex Teixeira and Fernandinho goals at the Donbass Arena, despite Oscar’s late consolation, as the Ukraine side deservedly took charge of Group E in the first of what could be a crucial double-header.
Chelsea were spared dropping out of the qualification places by Juventus’s shock draw at Nordsjaelland, but they will need to do much better at Stamford Bridge in two weeks to avoid doing so.
Terry’s first appearance since accepting his racism ban got off to the worst possible start as he unwittingly set up Shakhtar’s opener inside three minutes.
But he was arguably the least culpable Chelsea player on a night which cost the Barclays Premier League leaders dearly and a risible performance from Fernando Torres scuppered their hopes of a comeback.
The defeat was their first since their Uefa Super Cup thrashing by Atletico Madrid and the performance was almost as alarming at times as they were carved open by an outstanding Shakhtar side.
It was a nightmare start for Terry as the home side scored from their first attack after two minutes and 53 seconds, Luiz Adriano’s shot hitting the defender’s elbow and falling perfectly for Teixeira to slot past a helpless Petr Cech.
In what was a fiercely-contested game in a fizzing atmosphere, Oscar tried to respond with a tame low drive before Willian almost lived up to his manager’s promise to make Chelsea pay for not signing him by drilling wide.
That was in the 15th minute and it immediately got worse for the visitors when Frank Lampard went down injured, forcing an early end to his record 100th European appearance for the club and the introduction of Eden Hazard.
His early misfortune aside, Terry was having a stellar game, repeatedly reading attacks.
But he could not stop Willian brilliantly setting up Henrik Mkhitaryan, Ashley Cole doing enough to force Shakhtar’s goal machine to shoot too close to Cech.
That sparked a flurry of chaotic corners, which Chelsea defended frantically and saw Cech produce a wonder-save to deny Tomas Hubschman from point-blank range after Oscar inadvertently set up the midfielder.
Torres’s weak hooked volley from Branislav Ivanovic’s cross summed up a half in which he proved a real liability, a theme that continued after the restart.
Chelsea were otherwise looking capable of equalising, Juan Mata firing over after good work from Hazard, who immediately produced a horrendous gaffe to gift Shakhtar their second goal in the 52nd minute.
He was pickpocketed in the centre-circle by Fernandinho, who fed Adriano and both raced goalwards for the former to slot past Cech.
Torres was finally withdrawn for Daniel Sturridge with 20 minutes remaining and Mkhitaryan twice went close to making it 3-0.
David Luiz and Hubschman were both booked in the closing stages, which saw Oscar set up a tense finish two minutes from time when he swept home Ivanovic’s cross.
SHAKHTAR DONETSK: Pyatov, Srna, Kucher, Rakitskiy, Rat, Hubschman, Fernandinho, Alex Teixeira (Ilsinho 82), Mkhitaryan, Willian (Douglas Costa 88),Luiz Adriano.
CHELSEA: Cech, Ivanovic, Terry, Luiz, Cole, Oscar, Ramires, Mikel, Lampard (Hazard 18),Mata, Torres (Sturridge 70).
Referee: Damir Skomina (Slovenia).