The FTLS (femtosecond laser-induced thermal lens spectroscopy) technique was utilized to explore the photothermal response and heat transfer dynamics in various water-based binary mixtures containing monohydric and polyhydric alcohols. Our results highlight the significant influence of intermolecular hydrogen bonding interactions and the molecular properties of the mixture constituents on the photothermal behaviour of both pure solvents and their binary mixtures. Notably, we observed distinct effects of water inclusion on the heat transfer characteristics of monohydric alcohols (such as methanol and ethanol) compared to polyhydric alcohols (such as ethylene glycol (Etg) and glycerol (Gly)). This discrepancy can be attributed to the formation of unique molecular structures via hydrogen bonding interactions, which effectively hinders the natural molecular dynamics of short-chain length alcohols. Conversely, polyhydric alcohols like Etg and Gly exhibit contrasting photothermal characteristics due to their extensive intermolecular hydrogen bonding. Our investigations reveal that molecular attributes, such as chain length and the number of hydroxyl (-OH) groups, play a crucial role in altering the heat transfer mechanisms and thermal lens signal characteristics of the mixtures. These findings emphasize the sensitivity of FTLS as a probe for understanding the effects of intermolecular hydrogen bonding interactions on the molecular dynamics and thermo-optical properties of aqueous-alcoholic solutions.