The recent infrared detection of fullerenes (C60 and C70) in Planetary Nebulae (PNe) and R Coronae Borealis (RCB) stars offers a beautiful opportunity for studying the diffuse interstellar bands (DIBs) in sources where fullerenes are abundant. Here we present for the first time a detailed inspection of the optical spectra of the hot RCB star DY Cen and two fullerene PNe (Tc 1 and M 1-20), which permits us to directly explore the fullerenes - DIB connection. The DIB spectrum of DY Cen (García-Hernández et al. 2012a) is remarkably different from that in fullerene PNe (García-Hernández & Díaz-Luis 2013). In particular, Tc 1 displays unusually strong 4428 Å and 6309 Å DIBs, which are normal (or not seen) in DY Cen. On the other hand, DY Cen displays an unusually strong 6284 Å DIB that is found to be normal in fullerene PNe. We also report the detection of new broad and unidentified features centered at 4000 Å and 6525 Å in DY Cen and Tc 1, respectively. We suggest that the new 4000 Å band seen in DY Cen may be related to the circumstellar proto-fullerenes seen at infrared wavelengths (García-Hernández et al. 2012a). However, the intense 4428 Å DIB (probably also the 6309 Å DIB and the new 6525 Å band) may be related to the presence of larger fullerenes (e.g., C80, C240, C320, and C540) and buckyonions (multishell fullerenes such as C60@C240 and C60@C240@C540) in the circumstellar envelope of Tc 1 (García-Hernández & Díaz-Luis 2013).