The effects of nitrogen dioxide on the semiconductivity of crown-ether-substituted phthalocyanines and related aza-crown phthalocyanines in both dry and humid conditions are reported, for films deposited from chloroform solution and doped with different metal salts. Humidity changes the response to NO2 from a p-type conductivity increase to an n-type decrease. Replacing one oxygen atom in each crown ring by N-acetyl blocks the crown cavity and minimises effects of water and added salts. Replacing more oxygens with N-tosyl groups leads to strong steric effects and very poor conductivity in all environments. The effects of doping with other metal salts are also discussed.