A systematic steady-state fluorescence and time-resolved flash photolytic investigation of a series of covalently linked fullerene/ferrocene based donor-bridge-acceptor dyads is reported as a function of the nature of the spacer between the donor site (ferrocene) and acceptor site (fullerene) and the dielectric constant of the medium. The fluorescence of the investigated dyads 2 (Phi(rel) = 0.17 x 10(-4)), 3 (Phi(rel) = 0.78 x 10(-4)), 4 (Phi(rel) = 1.5 x 10(-4)), 5 (Phi(rel) = 0.7 x 10(-4)), and 6 (Phi(rel) = 2.9 x 10(-4)) in methylcyclohexane at 77 K were substantially quenched, relative to N-methylfulleropyrrolidine 1 (Phi(rel) = 6.0 x 10(-4)), indicating intramolecular quenching of the fullerene excited singlet state. Excitation of N-methylfulleropyrrolidine revealed the immediate formation of the excited singlet state, with lambda(max) around 886 nm. A rapid intersystem crossing (tau(1/2) = 1.2 ps) to the excited triplet state was observed with characteristic absorption around 705 nm. Picosecond resolved photolysis of dyads 2-6 in toluene showed light-induced formation of the excited singlet state which undergoes rapid intramolecular quenching, with rate constants of 28 x 10(9) s(-1), 6.9 x 10(9) s(-1), 3.4 x 10(9) s(-1), 14 x 10(9) s(-1), and 2.3 x 10(9) s(-1), respectively. Nanosecond-resolved photolysis of dyads 3 and 4 in degassed benzonitrile revealed long-lived charge separated states (tau(1/2) = 1.8 mu s (3) and tau(1/2) = 2.5 mu s (4)) with characteristic fullerene radical-anion bands at lambda(max) = 1055 nm. The nature of the spacer between C-60 and ferrocene, weak electronic ground-state interactions, steady-state fluorescence, and picosecond-resolved photolysis suggest two different quenching mechanism : through-bond electron transfer for dyads 2, 5, and 6 and formation of a transient intramolecular exciplex for dyads 3 and 4.