A multifunctional lab-on-a-chip platform for spectroscopic analysis of liquid samples based on an optofluidic jet waveguide is reported. The optofluidic detection scheme is achieved through the total internal reflection arising in a liquid jet of only 150 μm diameter, leading to highly efficient signal excitation and collection. This results in an optofluidic chip with an alignment-free spectroscopic detection scheme, which avoids any background from the sample container. This platform has been designed for multiwavelength fluorescence and Raman spectroscopy. The chip integrates a recirculation system that reduces the required sample volume. The evaluation of the device performance has been accomplished by means of fluorescence measurements performed on eosin Y in water solutions, achieving a limit of detection of 33 pM. The sensor has been applied in Raman spectroscopy of water-ethanol solutions, leading to a limit of detection of 0.18%. As additional application, analysis of riboflavin using fluorescence detection demonstrates the possibility of detecting this vitamin at the 560 pM level (0.21 ng l-1). Although measurements have been performed by means of a compact and low-cost spectrometer, in both cases the micro-jet optofluidic chip achieved similar performances if not better than high-end benchtop based laboratory equipment. This approach paves the way towards portable lab-on-a-chip devices for high sensitivity environmental and biochemical sensing, using optical spectroscopy.