The marriage of colloidal semiconductor nanocrystals and functional organic molecules has brought unique opportunities in emerging photonic and optoelectronic applications. Traditional semiconductor nanocrystals have been widely demonstrated to initiate efficient triplet energy transfer at the nanocrystal-acene interface. Herein, we report that unlike conventional semiconductor nanocrystals, lead halide perovskite nanocrystals promote an efficient Dexter-like singlet energy transfer to surface-anchored pentacene molecules rather than triplet energy transfer. Subsequently, molecular pentacene triplets are efficiently generated via singlet fission on the nanocrystal surface. Our demonstrated strategy not only unveils the obscure energy dynamics between perovskite nanocrystal and acenes, but also brings important perspectives of utilizing singlet fission throughout the solar spectrum.