It is an open, spreading shrub, growing up to 4 m (13 ft) tall with deeply divided leaves with linear lobes, and fawn flowers with a maroon to red style.

[6] Grevillea caleyi was first formally described in 1830 by Robert Brown in Supplementum primum prodromi florae Novae Hollandiae.

[6][10][11][12] Caley's grevillea is restricted to an area of 64 km2 (25 sq mi) in the suburbs of Terrey Hills, Belrose and Ingleside, and the endangered ecological community of Duffys Forest.

It grows in woodland on iron-rich laterite sandstone soils on ridgetops between elevations of 170 to 240 metres (560 to 790 ft) above sea level in open forest.

[1][4][13][14] Species commonly associated with G. caleyi include the trees Corymbia gummifera, Eucalyptus sieberi, Eucalyptus haemastoma, Banksia serrata and Xylomelum pyriforme, the shrubs Acacia myrtifolia, Banksia spinulosa, Conospermum longifolium, Grevillea buxifolia, Hakea dactyloides, Lambertia formosa, Pimelea linifolia and Telopea speciosissima and herbaceous plants including Anisopogon avenaceus, Dampiera stricta, Lomandra glauca, Lomandra obliqua and Pteridium esculentum.

[13] Grevillea caleyi is killed by fire, and since it does not form a lignotuber and does not propagate by suckering, it relies entirely on seed that is stored in the soil for regeneration.

Through casual observations, the likely common pollinators for this species include honeyeaters such as New Holland, white-eared and white cheeked, silvereyes, Little wattlebirds and Eastern spinebills.

[12] An assessment published by the IUCN in 2020 estimated the current extent of occurrence (EOO) of this species to be 37 km2 and the area of occupancy at 8 km2.

Fire is believed to play an important role in the recruitment process, as mature plants are uncommon in sites which have remained unburned for 15-20 years and seedlings sprout prolifically following bushfire events.

), Crofton weed (Ageratina adenophora) Blackberry (Rubus anglocandicans), Pampas Grass (Cortaderia selloana), Cotoneaster sp.