We report transient photoinduced absorption (t-PA) and magnetic field ( B)-dependent t-PA (t-MPA( B)) in a pristine low band gap π-conjugated copolymer composed of donor and acceptor moieties, namely, the poly[[4,8-bis[(2-ethylhexyl)oxy]benzo[1,2-b:4,5-b']dithiophene-2,6-diyl][3-fluoro-2-[(2-ethylhexyl)carbonyl]thi-eno[3,4- b]thiophenediyl]]) (or PTB7) used in photovoltaic applications. Unlike traditional π-conjugated polymers in which the primary photoexcitations are singlet excitons (SE), in pristine PTB7 we find at short times coexistence of two primary photoexcitation species, namely, SE and triplet-triplet (TT) pair. Both species are photogenerated directly from the ground state and are spin-correlated. Although the TT pair decomposes into two separate triplet excitons (TEs) in ∼100 ps, the separated TE spins are still entangled up to ∼6 μs. At longer times, the t-MPA( B) response of the surviving TEs shows transient narrowing effect, which is attributed to a distribution of the TE size.