Triplet excited states (triplets) serve as key intermediates in critical technologies and processes ranging from organic synthesis to biomedicine to molecular electronics. Production of triplets of p-conjugated organic molecules without heavy atoms remains challenging. Spin-orbit, charge-transfer intersystem crossing (SOCT-ISC) directly converts singlet charge-separated states to triplets in an electron donor-acceptor (D-A) pair. Here, using a series of orthogonal D-A type boron dipyrromethene (BODIPY) derivatives as a model system, we show that the formation of triplets is largely controlled by the spin-allowed transitions rather than by SOCT-ISC. Yet, the SOCT-ISC process can still proceed much faster than ordinary ISC between (p, p*) states because the spin-orbit coupling of SOCT-ISC is 2 orders of magnitude stronger. We further show that such a process can produce triplets in a non-triplet-forming molecule, perylene. Our findings reveal a clear physical basis for this spin-forbidden process and provide guidelines for future molecular designs exploiting the process.