The optical properties of different erbium (Er)-doped polydentate hemispherand organic cage complexes are studied, for use in polymer-based planar optical amplifiers. Room temperature photoluminescence at 1.54 um is observed, due to an intra-4 f transition in Er31. The Er is directly excited into one of the 4 f manifolds (at 488 nm), or indirectly (at 287 nm) via the aromatic part of the cage. The luminescence spectrum is 70 nm wide (full width at half maximum), the highest known for any Er-doped material, enabling high gain bandwidth for optical amplification. The absorption cross section at 1.54 um is 1.1x10 -20 cm2, higher than in most other Er-doped materials, which allows the attainment of high gain. Measurements were performed on complexes in KBr tablets, in which the complex is present in the form of small crystallites, or dissolved in the organic solvents dimethylformamide and butanol-OD. In KBr the luminescence lifetime at 1.54 um is <0.5 us, possibly due to concentration quenching effects. In butanol-OD solution, the lifetime is 0.8 us, still well below the radiative lifetime of 4 ms estimated from the measured absorption cross sections. Experiments on the selective deuteration of the near-neighbor C–H bonds around the Er3+-ion indicate that these are not the major quenching sites of the Er31 luminescence. Temperature dependent luminescence measurements indicate that temperature quenching is very small. It is therefore concluded that an alternative luminescence quenching mechanism takes place, presumably due to the presence of O–H groups on the Er-doped complex (originating either from the synthesis or from the solution). Finally a calculation is made of the gain performance of a planar polymer waveguide amplifier based on these Er complexes, resulting in a threshold pump power of 1.4 mW and a typical gain of 1.7 dB /cm.