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The thermopower and the electrical resistivity of [BiCaO2]2[CoO2]1.69 and corresponding iodine intercalated single crystals have been measured. Upon intercalation, the thermopower is drastically decreased, indicating that there is a hole doping by charge transfer from the intercalated iodine layer to the hexagonal CoO2 layer. The resistivity is increased due to stacking faults and disordered structures. Structural analyses confirmed the stacking scheme along the c direction, with the localisation of iodine between the [BiO] double layers. The effect of intercalation on the thermoelectric properties suggested discussions from the view point of hole doping and nano-block layer coupling effect.