Several acetylene bridged porphyrin–monophthalocyaninato ytterbium(III) hybrids, PZn–PcYb, PH₂–PcYb and PPd–PcYb, have been prepared and characterized by ¹H and ³¹P NMR, mass spectrometry, and UV-vis spectroscopy. Their photophysical and photochemical properties, especially the relative singlet oxygen (¹O₂) quantum yields and the two-photon absorption cross-section (σ₂), were investigated. These three newly synthesized compounds exhibited very large σ₂ values and substantial ¹O₂ quantum yields upon photo-excitation, making them potential candidates as one- and two-photon photodynamic therapeutic agents.