Phenylene oligomers represent a borderline case between very strongly π-conjugated molecular wires such as oligo-p-phenylene vinylenes and saturated molecular bridges. Even subtle chemical modifications of phenylene oligomers can therefore have a strong impact on charge transfer rates and mechanisms. On the basis of recently published selected case studies, this tutorial review discusses the key factors that affect charge transfer kinetics in phenylene oligomers with particular focus on the role of donor–bridge energy matching. Selected examples of triplet–triplet energy transfer reactions across phenylene oligomers are also discussed.