This paper reports the successful synthesis of the low symmetry phthalocyanines: metal-free 2,3-bis[2′-(2′′-hydroxyethoxy)ethoxy]-9,10,16,17,23,24-hexa-[Formula: see text]-butoxyphthalocyanine 1H[Formula: see text] and its zinc complex 1Zn along with their nonlinear optical (NLO) behavior in solution and in thin films. 1H NMR investigations evidenced of higher dissymmetry of electronic density in 1H[Formula: see text] in comparison with 1Zn. This dissymmetry is responsible for unusually higher values of Im[[Formula: see text]]/[Formula: see text], [Formula: see text], and [Formula: see text] for 1H[Formula: see text]in contrast to 1Zn, where the notable effect of heavy-metal enhancement of ISC was expected. Both compounds showed Im[[Formula: see text]]/[Formula: see text] values of the order of 10[Formula: see text] in chloroform which are higher in comparison to the symmetrical octabutoxyphthalocyanine H2[(BuO)8Pc]. NLO properties of 1H[Formula: see text] were improved via its incorporation into polycarbonate polymeric matrix together with CdSe@CdS-TOPO quantum dots. In such composite the value of Im[[Formula: see text]]/[Formula: see text] was almost three times higher in comparison with 1H[Formula: see text] solution in chloroform. The obtained composites are expected to be perspective components of optical materials, capable of protection against strong light irradiation.