The highly oriented macroporous graphene monoliths hybridized with carbon-coated metal oxide or phosphate (C/M/GM) with core/shell structure were fabricated by an ice-templating co-assembly of M/GO nanosheets (metal oxide/phosphates decorated graphene oxide) and polyvinyl alcohol (PVA), and following thermal treatment. With either tin oxide (SnO2) or iron phosphate (FePO4), the resulting C/M/GMs possess periodic macropores with diameters ranging from 5 to 20μm and high loading contents of active components (~70wt%). Served as the anode in LIBs, C/SnO2/GM maintains an ultrahigh capacity of 1665mAhg−1 at a current density of 0.2Ag−1 for 200 cycles. Even at an ultrafast charge rate of 10Ag−1, a decent capacity of 300mAhg−1 can still be achieved, with excellent cycling stability. And C/FePO4/GM also delivers a highly reversible capacity of 175mAhg−1 at a current density of 0.05Ag−1 for 150 cycles and a good capacity of 57mAhg−1 at 2Ag−1 when as the LIB cathode electrode.