The thin-film technology is the most promising technology to achieve a significant cost reduction in solar electricity. Laser scribing is an important step to preserve high efficiency of photovoltaic devices on large areas. The high-repetition-rate laser with the pulse duration of 10 ps was applied in selective ablation of multilayer thin-film a-Si solar cells deposited on flexible and rigid substrates. Two types of solar cells with flexible and rigid substrates have been investigated. The first type of solar cells was made of 400 nm a-Si layer coated on both sides with 2 $\mu $m transparent ZnO:Al contact layers deposited by CVD technique on the glass plate. The second type of solar cells was made of a flexible polyimide substrate coated with the Al back-contact, a-Si light absorbing layer and the ITO top-contact. Selection of the right laser wavelength is important to keep the energy coupling in a well defined volume at the interlayer interface. Well-defined shapes of scribes were produced by laser ablation through layers of the solar cell on the glass substrate. Localization of the coupled energy at the inner interface led to the “lift-off” type process rather than evaporation of the top ITO layer when the 355 nm radiation was applied. All laser scribes did not indicate any material melting or other thermal damage caused by laser irradiation. Ultra-short picosecond pulses ensured the high energy input rate into absorbing material therefore peeling of the layers had no influence on the remaining material.