After a two-year absence from the group stages, Kiev made a great start when Oleg Gusev scored after 20 minutes.
Porto were level three minutes later when Vincent Aboubakar outjumped his marker and he put the visitors in front after the break following a corner.
Buyalskyi saved Kiev though, racing onto Serhiy Rybalka's mis-hit drive and firing past Iker Casillas.
Brazilian striker Junior Moraes came close to opening the score for the hosts after seven minutes following a mistake by Casillas who dropped the ball from a corner.
Casillas had no chance 13 minutes later when Denys Garmash broke on the left and his pass fell at the feet of captain Gusev in the middle of the penalty area and he fired home.
Porto allowed no more than three minutes of joy for the home fans as Aboubakar headed in a perfect Miguel Layun cross.
Casillas showed his magic to parry a powerful snap shot from Garmash on the stroke of halftime.
Kiev, who suffered a huge loss a couple of hours before the
kickoff when Andriy Yarmolenko was ruled out with illness, were caught cold after 81 minutes when Aboubakar punished a poor clearance from keeper Olexandr Rybka.
Buyalskyi saved the day though to give Kiev heart for the rest of the campaign against English champions Chelsea and Maccabi Tel-Aviv.
(Editing by Martyn Herman)
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