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A series of La0.7K0.3− xSr xMnO3 (0.00 ≤  x ≤  0.3) films were fabricated on LaAlO3 substrates using a sol-gel spin-coating technique. The relationship between electrical transport properties and a microstructure was explained via the Jahn–Teller effect, a phenomenological percolation model, and a double-exchange mechanism. The results revealed the strong impact of K and Sr co-occupying A-sites on the formation of Mn3+/Mn4+ pairs, crystal structure, conductivity, surface morphology, and in-plane and out-of-plane strains. The as-fabricated La0.7K0.25Sr0.05MnO3 films showed a peak temperature coefficient of resistivity of 16.63% K−1 at 298.3 K.

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