We report electrical transport experiments on the colossal magnetoresistance compound (La,Ca͒MnO 3 over a wide range of composition and temperature. Comparison of thermopower and electrical resistivity measurements above the metal-insulator transition indicate a transport mechanism not dominated by spin disorder, but by small polaron formation. Additionally, we find that in the high-temperature limit the thermopower corresponds to backflow of spin entropy, expected from motion of positively charged particles in a rigid Sϭ2 system, showing a remarkable independence of Sϭ3/2 particle density. ͓S0163-1829͑97͒09334-X͔The recent observation of large magnetoresistance effects in thin films of doped LaMnO 3 has renewed the interest in the metal-insulator transition in these materials. [1][2][3] Since the metal-insulator transition temperature, T MI , can be tuned to above room temperature, this opens possibilities to use this material not only for recording media but also for other types of magnetic switching applications. However, the emerging notion that magnetoresistance due to a metal-insulator transition decreases with increasing T MI , necessitates a better understanding of the underlying basic transport mechanism to exploit the magnetoresistive properties of these materials fully. The microscopic nature of the transport mechanism is condensed into the description of double exchange, the simultaneous electron transfer of an electron on a Mn atom to an O atom of the surrounding oxygen octahedron, and another electron from this O atom to a neighboring Mn atom. 4 This indirect exchange mechanism establishes, because of spin conservation in the exchange, a direct relation of the metallic state with the ferromagnetic coupling between the Mn spins. However, there is remarkably little known about the transport mechanism in the insulating state. Whereas spin disorder can contribute to the variations in the resistivity near T c , only more recently the role of electron-phonon interactions on the localization has been put in a clearer perspective. [5][6][7] This theoretical work was based on research on magnetic semiconductors like EuO, and only recently applied to doped LaMnO 3 . Still, it is not known if the metal insulator transition in doped LaMnO 3 is driven by changes in the carrier density or the mobility.In order to gain insight into the nature of the transport mechanism, we have performed thermopower measurements on doped LaMnO 3 over a wide range of concentrations and temperatures in addition to the basic characterization by electrical resistivity and magnetic measurements. Thermopower is in contrast to electrical resistivity relatively insensitive to effects of grain boundaries and disorder. We will show that for this material, thermopower provides unique insight into the transport mechanism. First, we show that the change of sign in the thermopower is not related to competition between electron and hole conduction, but accidental cancellation of the entropic term and the energy transport term of the thermopower...