Two pyrene-fused pyrazaacenes containing phenothiazine and phenoxazine units, 10-(phenanthro[4,5-abc]phenazin-11-yl)-10H-phenothiazine (Py-PTZ) and 10-(phenanthro[4,5-abc]phenazin-11-yl)-10H-phenoxazine (Py-PXZ), were successfully synthesized and their thermal, optical and electronic properties were investigated systematically. Both of them are nearly non-emissive in chloroform solution but become highly emissive in the mixed solution of chloroform and n-hexane and in the solid states. The solution-processed doped devices with a structure of ITO/PEDOT:PSS (30 nm)/CBP:Py-PTZ or Py-PXZ (x wt%) (25 nm)/TPBi (35 nm)/Liq (2 nm)/Al (150 nm) were fabricated, in which the Py-PTZ-based doped device exhibited a maximum luminance (Lmax) of 2570 cd/m2, a maximum current efficiency (CEmax) of 2.67 cd/A and a maximum external quantum efficiency (EQEmax) of 1.64%, and the Py-PXZ-based doped device showed Lmax, CEmax and EQEmax of 4554 cd/m2, 6.39 cd/A and 3.81%, respectively.