Long‐lived triplet excitons are kingmakers to generate high efficiency optoelectronic OLEDs. However, it is difficult to produce matrix‐free solid state emissive room temperature phosphorescence (RTP) from carbon dots (CDs). In the present work, limited rotation of the two naphthol rings in (R)‐1,1‐Bi‐2‐naphthol (R‐Binol) has been used to synthesize CDs aimed to obtain emission in the aggregated and RTP states. The R‐Binol‐derived CDs were prepared using an easy one‐pot solvothermal treatment of the precursor. In‐depth structural analysis reveals the presence of twisted naphthalene moiety that resists π‐π stacking to make it dual emissive. These CDs are prone to accumulate producing spherical aggregates with 32‐fold enhanced emission in binary THF‐water mixture. Nevertheless, for the first time, we harvested triplet excitons from matrix free CDs generating 23% PLQY. A phosphor converted light emitting diode (pc‐LED) was also fabricated with the CDs.