Two　new　tetra-　or　di-α-substituted　zinc(II)　phthalocyanines　5　and　6　have　been　prepared　through　a　＂side-strapped＂　method.　In　the　molecules,　the　adjacent　benzene　rings　of　the　phthalocyanine　core　are　linked　at　α-position　through　a　triethylene　glycol　bridge　to　form　a　hybrid　aza-/oxa-crown　ether.　The　tetra-α-substituted　phthalocyanine　5　shows　an　eclipsed　self-assembly　property　in　CH2Cl2　and　the　effect　on　the　di-α-substituted　analogue　6　is　significantly　weakened.　Furthermore,　the　crown　ethers　of　these　compounds　can　selectively　complex　with　Fe　3+　or　Cu2+　ion　in　DMF,　leading　to　formation　of　J-aggregated　nano-assemblies,　which　can　be　disaggregated　in　the　presence　of　some　organic　or　inorganic　ligands,　such　as　triethylamine,　tetramethylethylenediamine,　CH3COO-,　or　OH-.　In　addition,　both　compounds　are　efficient　singlet　oxygen　generators　with　the　singlet　oxygen　quantum　yields　(ΦΔ)　of　0.54-0.74　in　DMF　relative　to　unsubstituted　zinc(II)　phthalocyanine　(ΦΔ=0.56)　.　They　exhibit　photodynamic　activities　toward　HepG2　human　hepatocarcinoma　cells,　but　the　compound　6,　which　has　more　than　40-fold　lower　IC50　value　(0.08　μM)　compared　to　the　analogue　5　(IC50=3.31　μM),　shows　remarkablely　higher　in　vitro　photocytotoxicity　due　to　its　significantly　higher　cellular　uptake　and　singlet　oxygen　generation　efficiency.　The　results　suggest　that　these　compounds　can　serve　as　promising　multifunctional　materials　both　in　(opto)electronic　field　and　photodynamic　therapy.　Copyright　©　2013　WILEY-VCH　Verlag　GmbH　&　Co.　KGaA,　Weinheim.