Differential functional specialization of the left and right hemispheres for linguistic and emotional functions, respectively, suggest that interhemispheric communication via the corpus callosum is critical for emotional awareness. Accordingly, it has been hypothesized that the age-related decline in callosal connectivity mediates the frequently demonstrated reduction in emotional awareness in older age. The present study tests this hypothesis in a sample of 307 healthy individuals between 20-89 years using combined structural and diffusion-tensor magnetic resonance imaging (MRI) of the corpus callosum. As assumed, inter-hemispheric connectivity (midsagittal callosal area and thickness, as well as fractional anisotropy, FA) and emotional awareness (i.e., increase in externally-oriented thinking, EOT; assessed with the Toronto Alexithymia Scale, TAS-20) were found to be reduced in older (> 60 years) compared to younger participants. Furthermore, relating callosal measures to emotional awareness, FA in the genu of the corpus callosum was found to be negatively correlated with EOT in male participants. Thus, "stronger" structural connectivity (higher FA) was related with higher emotional awareness (lower EOT). However, a formal mediation analysis did not support the notion that age-related decline in emotional awareness is mediated by the corpus callosum. Thus, the observed reduction of emotional awareness and callosal connectivity in older age likely reflects parallel but not inter-dependent processes.