We report an electron spin resonance (ESR) study of single crystals of the spin-chain spin-ladder compound (Sr,La,Ca)_{14}Cu_{24}O_{41}. The data suggest that in intrinsically hole doped Sr_{14-x}Ca_xCu_{24}O_{41} only a small amount of holes is transferred from the chains to the ladders with increasing x, resulting in a crossover from spin dimerized to uniform spin chains. In the samples of La_{14-x}Ca_xCu_{24}O_{41} with reduced hole content a very broad signal is observed in the paramagnetic state, indicative of a surprisingly strong anisotropy of the nearest neighbor exchange in the chains.
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