We present the results of recent muon-spin rotation ( μSR) experiments on a variety of novel molecular magnetic systems. Muons are sensitive to local static fields and magnetic fluctuations, but can probe much more than just the onset of long-range magnetic order. The spin-crossover phenomenon has been studied in Fe(PM-PEA) 2(NCS) 2, which shows Gaussian and root-exponential muon relaxation in the high-spin and low-spin phases, respectively. Dy spin fluctuations have been studied with μSR in the ferrimagnetic chain Dy(hfac) 3(NITEt). Experiments on a disc-shaped molecular complex containing Fe 19 (with spin 31 2 ) reveal the effects of quantum tunneling of magnetization and allow an estimate of the quantum tunneling rate.