Here are your sentences revised for naturalness and correctness:
1. I saw you as I was at the cafe.
* This is mostly correct, but it would be more natural to say: "I saw you while I was at the cafe."
2. It started to rain just as I left home.
* "Leave" should be changed to "left" to match the past tense.
3. As I didn't have enough money for a taxi, I decided to walk.
* "Went to walk" should be changed to "decided to walk" for clarity.
4. Just as I took the picture, it started to rain.
* "It was rain" should be changed to "it started to rain" for correctness and clarity.
So the corrected sentences are:
1. I saw you while I was at the cafe.
2. It started to rain just as I left home.
3. As I didn't have enough money for a taxi, I decided to walk.
4. Just as I took the picture, it started to rain.