Two recently synthesized derivatives of porphycene, 2,7,12,17-tetramethyl-3,6-13,16-dibenzo porphycene and 2:7,12,17-tetra-tert-butyl-3,6-13,16-dibenzo[cde,mno]porphycene, were studied by stationary and time-resolved spectroscopy and quantum chemical calculations. Both compounds were found to be nonluminescent even at low temperatures. Picosecond transient absorption studies performed in solution at 293 K and in solid nitrogen matrices at 15 K revealed a rapid recovery of the ground-state bleaching. The rate of this process remains very high even at low temperatures. Possible reasons for this photophysical behavior are discussed, including nonplanarity and a fast excited-state cis-trans NH tautomerization. Electronic transitions of dibenzoporphycenes may be correlated with those of porphyrin and porphycene. However, an "intruder" state lies between the analogues of the Q and Soret bands.