Ultrafast measurements of transient excited-state absorption in the spectral region spanning the infrared active vibrational active (IRAV) modes in the prototypical luminescent polymers, poly(phenylene vinylene), PPV, and poly[2-methoxy-5-( 2-ethyl-hexyloxy)-(phenylene-vinylene)], MEH-PPV, reveal charge carrier generation within 100 fs after photoexcitation. The relatively large photocarrier quantum efficiency in MEH-PPV, phi(0) approximate to 0.1 in zero applied electric field, implies primary photogeneration of charge carriers. Comparison of the recombination dynamics in MEH-PPV and PPV indicates that the carrier recombination rate is sensitive to the strength of the inter-chain interaction.