The singlet fission (SF) process converts one high-energy singlet exciton to two low-energy triplet excitons after absorbing one photon. Organic photovoltaic devices based on the SF process have shown great potential in solar energy conversion to exceed Shockley-Queisser limit. The key to SF photovoltaic devices requires efficient electron transfer (ET) from triplet exciton after SF, which is yet to be thoroughly investigated. Here, we performed thorough photophysical studies in 6,13-Bis(triisopropylsilylethynyl)pentacene (TIPS-pentacene)/C-60 heterostructures using TIPS-pentacene microsize single crystal as a well-defined model system. We show the SF process in TIPS-pentacene single crystal occurs by a two-step process, with triplet pair intermediates forming in 75 fs and then dissociating to non-interacting triplets in 1.6 ps. The SF process in single crystal is comparable to that in polycrystalline film. Importantly, we observe a considerable fraction of singlet excitons is quenched by ultrafast (<75 fs) interfacial ET prior to fission and no ET from triplet excitons in 1.5 ns time window. We confirm that the absence of ET is not limited by exciton diffusion but due to very slow (>> 1.5 ns) interfacial ET from triplet exciton. The observations contradict expected singlet and triplet ET behaviors based on a simple two-state Marcus ET model and suggest long-range interfacial ET from delocalized photoexcitation. The ultrafast ET from singlet exciton before SF and slow ET from triplet exciton call for reconsideration and careful design of efficient SF photovoltaic devices.