Coupling of photophysical and photochemical techniques to microscopy eventu
ally assisted by manipulating techniques, such as laser trapping, has facil
itated obtaining information on heterogeneous organic and bio-organic syste
ms by mapping their optical and excited state properties. Scanning confocal
microscopy, eventually of laser trapped ensembles, coupled to fluorescence
decay analysis and imaging, scanning plate confocal and scanning near fiel
d optical microscopy provide combined spectral and spatial resolution down
to a few tenths of nanometers. An even better resolution can be achieved us
ing scanning tunneling microscopy. In this contribution a number of organic
and macromolecular systems are discussed first in solution and in a next s
tep assembled either in a trap or at a surface. The techniques are illustra
ted and their limits assessed using latex particles labeled with fluorophor
es. Time resolved spectroscopy in solution allows the evaluation of migrati
on of the excited state and the collapse of the arms in a dendritic structu
re. These and other macromolecular structures can be trapped and the obtain
ed assembly visualized and analyzed. Deposition by self-assembly provides t
he possibility using scanning near field optical microscopy to investigate
the excited state properties of ordered arrays. By dilution in a polymer fi
lm of dendritic structures single particle, single chromophore and single m
olecule spectroscopy becomes accessible. Scanning tunneling microscopy is s
uccessfully applied to illustrate the visualization and manipulation of str
uctures with subnanometer resolution and the study of their properties incl
uding stimulus by light induced transformations.