The challenge in today's bioaerosol monitoring is to retrieve real-time information on the qualitative and quantitative composition of the ambient air in bioparticles implicated to human health. A pilot study was conducted during March-May 2018 in Athens, Greece in order to detect bioparticles within the Planetary Boundary Layer (PBL) by implementing the LIF LiDAR (Laser-Induced Fluorescence Light Detection and Ranging) technique at an excitation wavelength of 266 nm in order to determine the major components' contribution on the total fluorescence LiDAR signals aloft (30-100 m above our site). The laboratory characterization of the prevalent pollen grains and fungal spores fluorescence signatures enabled through deconvolution the breaking down of the retrieved LIF LiDAR signals and unravelled each bioparticle's contribution. The bioaerosol occurrence and concentration, as determined by the concurrent sampling with a volumetric particle sampler, verified that the detected fluorescence is related to the fungal and pollen aerosol concentration. The results of this study are very promising for the implementation of remote sensing technology in routine detection and quantification of airborne bioparticles in real-time which is important for allergy sufferers and physicians.