Four novel [Formula: see text]-dialkylated porphycenes, [Formula: see text]. 2,12-(DEPoT and DPPoT) and 2,17-(DEPoC and DPPoC) were realized for the first time in porphycene chemistry. Unsymmetrically substituted monoalkylbipyrrole dialdehydes were subjected to McMurry coupling reactions to produce the isomeric [Formula: see text]-dialkylated porphycenes. All these porphycenes exhibit unexpectedly good solubility in common organic solvents. The positional effects of alkyl groups could be controlled through diversification in structure of porphycene cores and, as a result, their photophysical properties. DPPoT presents significant fluorescence accompanied by reasonable singlet oxygen generation ability.