The present invention relates to a process for preparing tertiary alkyl esters of (meth)acrylic acid having at least 4 carbon atoms in the alkyl radical. The process includes reacting (meth)acrylic acid with at least one olefin of formula (I) in homogeneous phase in the presence of an acidic catalyst in a reactor, discharging the resulting reaction mixture from the reactor, separating the discharged reaction mixture into a first mixture which contains the catalyst and a second mixture which contains the tertiary alkyl ester of (meth)acrylic acid having at least 4 carbon atoms in the alkyl radical, and removing the tertiary alkyl ester of (meth)acrylic acid having at least 4 carbon atoms in the alkyl radical from the second mixture in the presence of compound S, which comprises at least one N-oxyl group and is added as a stabilizer.