The analytical capabilities of the microminiaturised lab-on-a-valve (LOV) module integrated into a microsequential injection (muSI) fluidic system in terms of analytical chemical performance, microfluidic handling and on-line sample processing are compared to those of the micro total analysis systems (muTAS), also termed lab-on-a-chip (LOC). This paper illustrates, via selected representative examples, the potentials of the LOV scheme vis-à-vis LOC microdevices for environmental assays. By means of user-friendly programmable flow and exploitation of the interplay between the thermodynamics and the kinetics of the chemical reactions at will, LOV allows accommodation of reactions which, at least at the present stage, are not feasible by application of microfluidic LOC systems. Thus, in LOV one may take advantage of kinetic discriminations schemes, where even subtle differences in reactions are utilized for analytical purposes. Furthemore, it is also feasible to handle multi-step sequential reactions of divergent kinetics; to conduct multi-parametric determinations without manifold reconfiguration by utilization of the inherent open architecture of the micromachined unit for the implementation of peripheral modules and automated handling of a variety of reagents; and most importantly, it offers itself as a versatile front end to a plethora of detection schemes. Not the least, LOV is regarded as an emerging downscaled tool to overcome the dilemma of LOC microsystems to admit real-life samples. This is nurtured via its intrinsic flexibility for accommodation of sample pre-treatment schemes aimed at the on-line manipulation of complex samples.Thus, LOV is playing a prominent role in the environmental field, whenever the monitoring of trace level concentration of pollutants is pursued, because both matrix isolation and concentration of target analytes is most often imperative, or in fact necessary, prior to sample presentation to the detector.