Abstract Ultrafine CoAl 2 O 4 ceramic pigment is prepared by Pechini-sacrificial agent method (P-S) using nitrate as oxidant, glycine as fuel and active carbon as sacrificial agent. The obtained ceramic pigment was characterized by SEM, TEM, XRD and CIELAB colorimetric analysis. The results show that the ultrafine CoAl 2 O 4 powder has the mean particle size of 2–4 µm, which is the soft-aggregation of the primary crystals. The primary crystal of CoAl 2 O 4 powder is only 5–10 nm characterized by TEM, which is far finer than that prepared by normal Pechini method. The CIE parameter of CoAl 2 O 4 ceramic pigment is L *=41.76, b *=−6.57, a *=−45.01. The transparent glaze with 2 wt% CoAl 2 O 4 prepared by Pechini-sacrificial agent method added has the similar CIE parameter to that with 6 wt% CoAl 2 O 4 prepared by normal Pechini method added.