The development of new methods for determining at a very low level a large spectrum of substances affecting the behaviour of living organisms is still a challenging goal. For such a purpose, chemical sensors which can be defined as the intimate combination of a sensitive and specific layer with a transducer, are undoubtedly among the more promising devices. In this field, optical sensors are expanding rapidly, mainly based on absorption, fluorescence, chemi- and bioluminescence. Beside pH and gases, drugs (anticonvulsant, antitumour, anaesthetic...) and other compounds of biological interest can be determined with specifically designed optical sensors, for instance immunosensors. Special attention will be given to optical biosensors with emphasis on chemi- and bioluminescence-based devices which are highly selective and ultrasensitive. When co-immobilizing various auxiliary enzymes in the sensing layer, the potentialities of such devices can be greatly extended as demonstrated by promising results recently obtained in our group.