The impacts of solvent and thermal annealing on the mobility and photogeneration efficiency of free charge carriers in regioregular poly(3-hexylthiophene) were investigated by flash-photolysis time-resolved microwave conductivity measurements, transient absorption spectroscopy of the perylenediimide radical anion, and photocurrent measurements of a comb-type interdigitated electrode. A respectable high mobility of 0.62 cm(2)V(-1) s(-1) was found as a three-dimensional value, highlighting the unprecedented electronic nature of the conjugated polymer.