Let's assume for a moment that you are talking about alkenes... In principle, the E and Z isomers should have different properties (dipol moment, van der Waals properties, etc) which should be reflected by different retention times on a C-18 column. However, the question is: how big the differences are... Column length and mobile phase will be two important parameters here. In particular, acidic modifiers of the mobile phase (like AcOH or TFA, make sure there is no E/Z isomerization occurring on the column) can be helpful. Some transition metal salts can also be used but, again, one needs to be able to exclude the E/Z isomerization. Thus, it all depends on the particular case.